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Results for “diabatic states”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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NASA NTRS2002

Prospects for Improved Forecasts of Weather and Short-Term Climate Variability on Subseasonal (2-Week to 2-Month) Times Scales

This workshop, held in April 2002, brought together various Earth Sciences experts to focus on the subseasonal prediction problem. While substantial advances have occurred over the last few decades in both weather and seasonal prediction, progress in improving predictions on these intermediate time scales (time scales ranging from about two weeks to two months) has been slow. The goals of the workshop were to get an assessment of the "state of the art" in predictive skill on these time scales, to determine the potential sources of "untapped" predictive skill, and to make recommendations for a course of action that will accelerate progress in this area. One of the key conclusions of the workshop was that there is compelling evidence for predictability at forecast lead times substantially longer than two weeks. Tropical diabatic heating and soil wetness were singled out as particularly important processes affecting predictability on these time scales. Predictability was also linked to various low-frequency atmospheric "phenomena" such as the annular modes in high latitudes (including their connections to the stratosphere), the Pacific/North American (PNA) pattern, and the Madden Julian Oscillation (MJO). The latter, in particular, was highlighted as a key source of untapped predictability in the tropics and subtropics, including the Asian and Australian monsoon regions.

Schubert, Siegfried↗

DOE OSTI2021

Full-dimensional quantum stereodynamics of the non-adiabatic quenching of OH(A2Σ+) by H2

Abstract The Born–Oppenheimer approximation, assuming separable nuclear and electronic motion, is widely adopted for characterizing chemical reactions in a single electronic state. However, the breakdown of the Born–Oppenheimer approximation is omnipresent in chemistry, and a detailed understanding of the non-adiabatic dynamics is still incomplete. Here we investigate the non-adiabatic quenching of electronically excited OH(A 2 Σ + ) molecules by H 2 molecules using full-dimensional quantum dynamics calculations for zero total nuclear angular momentum using a high-quality diabatic-potential-energy matrix. Good agreement with experimental observations is found for the OH(X 2 Π) ro-vibrational distribution, and the non-adiabatic dynamics are shown to be controlled by stereodynamics, namely the relative orientation of the two reactants. The uncovering of a major (in)elastic channel, neglected in a previous analysis but confirmed by a recent experiment, resolves a long-standing experiment–theory disagreement concerning the branching ratio of the two electronic quenching channels.

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DOE OSTI2020

Nonadiabatic Electronic Energy Transfer in Chemical Oxygen-Iodine Laser: Powered by Derivative Coupling or Spin-Orbit Coupling?

Derivative couplings near a conical intersection and spin-orbit couplings between different spin states are known to facilitate nonadiabatic transitions in molecular systems. In this report, we investigate a prototypical electronic energy transfer process, I( 2 P 3/2 )+O 2 (a 1 Δ g )→I( 2 P 1/2 )+ O 2 (X 3 Σ g - ), which is of great importance for the chemical oxygen-iodine laser. To understand the nonadiabatic dynamics, this multistate process is investigated in full dimensionality with quantum wave packets using diabatic potential energy surfaces coupled by both derivative and spin-orbit couplings, all determined from first principles. A near quantitative agreement with structural, energetic, and kinetic measurements is achieved. Detailed analyses suggest that the nonadiabatic dynamics is largely controlled by derivative coupling near conical intersections, which leads to a small effective barrier and hence a slightly positive temperature dependence of the rate coefficient. The new findings should extend our understanding of energy transfer, provide a quantitative basis for numerical simulations of the chemical oxygen-iodine laser, and have important implications in other electronic energy transfer processes.

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NASA NTRS1989

Explosive east coast cyclogenesis - Numerical experimentation and model-based diagnostics

Numerical experimentation of explosive east-coast cyclogenesis is performed using the Florida State University Global Spectral Model (FSUGSM). The three cases examined here are the Presidents' Day storm of February 18-19, 1979 and the North Atlantic and Pacific bombs of January 18-20, 1979 which formed off the east coasts of the United States and Japan, respectively. The use of a global model provides a framework for studying the phenomena on the 3-5 day time scale. The forecast verifications of the numerical experiments indicate that the FSUGSM was able to adequately predict the phase, intensity, and synoptic-scale structure. These results justify the use of model data for diagnostic studies of the bomb. The model data are used to quantify the role of the adiabatic and diabatic forcing in the explosive cyclogenetic process, using surface pressure tendency to gage development.

Manobianco, John↗

NASA NTRS1991

Linear stability of free planetary waves in the presence of radiative-photochemical feedbacks

The diabatic effects of Newtonian cooling and ozone-dynamics interaction on the linear stability of free planetary waves in the atmosphere have been studied using a simple beta-plane model. The model couples radiative transfer, ozone advection, and ozone photochemistry with the quasi-geostrophic dynamical circulation. An analytical expression is derived which demonstrates the following: (1) the influence of meridional ozone advection on wave growth or decay depends on the wave and basic state vertical structures; and (2) photochemically accelerated cooling, which predominates in the upper stratosphere, augments the Newtonian cooling rate and is stabilizing. Attention is also given to the 1D linear stability problem which is numerically solved for a Charney basic state and for zonal mean basic states. It is shown that ozone heating generated by ozone-dynamics interaction in the stratosphere can reduce (enhance) the damping rates due to Newtonian cooling by as much as 50 percent for planetary waves of large vertical scale and maximum amplitude in the stratosphere.

Nathan, Terrence R.↗

DOE OSTI2026

Charge Transport in Solvated Donor–Acceptor Functionalized Peptoids: Molecular Dynamics and Rate Theory

Scalable solar-energy conversion requires photoactive materials that combine the efficiency of natural photosynthetic systems with the stability and processability needed for practical applications. Achieving reliable charge transport in soft, self-assembled organic materials remains challenging, as structural fluctuations and environmental effects strongly influence charge-transfer (CT) rates. Here, we present a broadly applicable computational framework for evaluating CT rates in the condensed phase, combining Fermi’s golden rule rate theory with inputs from all-atom molecular dynamics (MD) simulations and first-principles electronic-structure calculations. The approach does not rely on system-specific parametrization and is applicable to a wide range of soft and disordered materials. We demonstrate the applicability and usefulness of the framework on redox-active peptoids functionalized with iron–porphyrin (Fe–P) complexes, a bioinspired platform with programmable donor–acceptor units and tunable three-dimensional organization. The calculated CT rates exhibit strong sensitivity to molecular conformation, with variations spanning several orders of magnitude. This dependence is shown to arise from the pronounced variation in diabatic electronic coupling with the relative orientations and separations of the Fe–P complexes across the conformational ensemble. The framework provides a consistent route for connecting atomistic structure to CT kinetics in the condensed phase and enables analysis of structure–rate relations in organic semiconducting systems.

Charge transfer↗

DOE OSTI2020

On the proper derivation of the Floquet-based quantum classical Liouville equation and surface hopping describing a molecule or material subject to an external field

We investigate different approaches to derive the proper Floquet-based quantum–classical Liouville equation (F-QCLE) for laser-driven electron-nuclear dynamics. The first approach projects the operator form of the standard QCLE onto the diabatic Floquet basis and then transforms to the adiabatic representation. The second approach directly projects the QCLE onto the Floquet adiabatic basis. Both approaches yield a form that is similar to the usual QCLE with two modifications: (1) The electronic degrees of freedom are expanded to infinite dimension and (2) the nuclear motion follows Floquet quasi-energy surfaces. However, the second approach includes an additional cross derivative force due to the dual dependence on time and nuclear motion of the Floquet adiabatic states. Our analysis and numerical tests indicate that this cross derivative force is a fictitious artifact, suggesting that one cannot safely exchange the order of Floquet state projection with adiabatic transformation. Our results are in accord with similar findings by Izmaylov et al., [J. Chem. Phys. 140, 084104 (2014)] who found that transforming to the adiabatic representation must always be the last operation applied, although now we have extended this result to a time-dependent Hamiltonian. Finally, this paper and the proper derivation of the F-QCLE should lay the basis for further improvements of Floquet surface hopping.

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NASA NTRS2012

Life Cycle of Midlatitude Deep Convective Systems in a Lagrangian Framework

Deep Convective Systems (DCSs) consist of intense convective cores (CC), large stratiform rain (SR) regions, and extensive non-precipitating anvil clouds (AC). This study focuses on the evolution of these three components and the factors that affect convective AC production. An automated satellite tracking method is used in conjunction with a recently developed multi-sensor hybrid classification to analyze the evolution of DCS structure in a Lagrangian framework over the central United States. Composite analysis from 4221 tracked DCSs during two warm seasons (May-August, 2010-2011) shows that maximum system size correlates with lifetime, and longer-lived DCSs have more extensive SR and AC. Maximum SR and AC area lag behind peak convective intensity and the lag increases linearly from approximately 1-hour for short-lived systems to more than 3-hours for long-lived ones. The increased lag, which depends on the convective environment, suggests that changes in the overall diabatic heating structure associated with the transition from CC to SR and AC could prolong the system lifetime by sustaining stratiform cloud development. Longer-lasting systems are associated with up to 60% higher mid-tropospheric relative humidity and up to 40% stronger middle to upper tropospheric wind shear. Regression analysis shows that the areal coverage of thick AC is strongly correlated with the size of CC, updraft strength, and SR area. Ambient upper tropospheric wind speed and wind shear also play an important role for convective AC production where for systems with large AC (radius greater than 120-km) they are 24% and 20% higher, respectively, than those with small AC (radius=20 km).

Feng, Zhe↗

NASA NTRS2017

Synoptic Traveling Weather Systems on Mars: Effects of Radiatively-Active Water Ice Clouds

Atmospheric aerosols on Mars are critical in determining the nature of its thermal structure, its large-scale circulation, and hence the overall climate of the planet. We conduct multi-annual simulations with the latest version of the NASA Ames Mars global climate model (GCM), gcm2.3+, that includes a modernized radiative-transfer package and complex water-ice cloud microphysics package which permit radiative effects and interactions of suspended atmospheric aerosols (e.g., water ice clouds, water vapor, dust, and mutual interactions) to influence the net diabatic heating. Results indicate that radiatively active water ice clouds profoundly affect the seasonal and annual mean climate. The mean thermal structure and balanced circulation patterns are strongly modified near the surface and aloft. Warming of the subtropical atmosphere at altitude and cooling of the high latitude atmosphere at low levels takes place, which increases the mean pole-to-equator temperature contrast (i.e., "baroclinicity"). With radiatively active water ice clouds (RAC) compared to radiatively inert water ice clouds (nonRAC), significant changes in the intensity of the mean state and forced stationary Rossby modes occur, both of which affect the vigor and intensity of traveling, synoptic period weather systems. Such weather systems not only act as key agents in the transport of heat and momentum beyond the extent of the Hadley circulation, but also the transport of trace species such as water vapor, water ice-clouds, dust and others. The northern hemisphere (NH) forced Rossby waves and resultant wave train are augmented in the RAC case: the modes are more intense and the wave train is shifted equatorward. Significant changes also occur within the subtropics and tropics. The Rossby wave train sets up, combined with the traveling synoptic period weather systems (i.e., cyclones and anticyclones), the geographic extent of storm zones (or storm tracks) within the NH. A variety of circulation features will be presented which indicate contrasts between the RAC and nonRAC cases, and which highlight key effects radiatively-active clouds have on physical and dynamical processes active in the current climate of Mars.

Atmospheric aerosols↗

NASA NTRS2017

Synoptic Traveling Weather Systems on Mars: Effects of Radiatively-Active Water Ice Clouds

Atmospheric aerosols on Mars are critical in determining the nature of its thermal structure, its large-scale circulation, and hence the overall climate of the planet. We conduct multi-annual simulations with the latest version of the NASA Ames Mars global climate model (GCM), gcm2.3+, that includes a modernized radiative-transfer package and complex water-ice cloud microphysics package which permit radiative effects and interactions of suspended atmospheric aerosols (e.g., water ice clouds, water vapor, dust, and mutual interactions) to influence the net diabatic heating. Results indicate that radiatively active water ice clouds profoundly affect the seasonal and annual mean climate. The mean thermal structure and balanced circulation patterns are strongly modified near the surface and aloft. Warming of the subtropical atmosphere at altitude and cooling of the high latitude atmosphere at low levels takes place, which increases the mean pole-to-equator temperature contrast (i.e., "baroclinicity"). With radiatively active water ice clouds (RAC) compared to radiatively inert water ice clouds (nonRAC), significant changes in the intensity of the mean state and forced stationary Rossby modes occur, both of which affect the vigor and intensity of traveling, synoptic period weather systems.Such weather systems not only act as key agents in the transport of heat and momentum beyond the extent of the Hadley circulation, but also the transport of trace species such as water vapor, water ice-clouds, dust and others. The northern hemisphere (NH) forced Rossby waves and resultant wave train are augmented in the RAC case: the modes are more intense and the wave train is shifted equatorward. Significant changes also occur within the subtropics and tropics. The Rossby wave train sets up, combined with the traveling synoptic period weather systems (i.e., cyclones and anticyclones), the geographic extent of storm zones (or storm tracks) within the NH. A variety of circulation features will be presented which indicate contrasts between the RAC and nonRAC cases, and which highlight key effects radiatively-active clouds have on physical and dynamical processes active in the current climate of Mars.

GCM-global climate model↗

NASA NTRS2016

Synoptic Traveling Weather Systems on Mars: Effects of Radiatively-Active Water Ice Clouds

Atmospheric aerosols on Mars are critical in determining the nature of its thermal structure, its large-scale circulation, and hence the overall climate of the planet. We conduct multi-annual simulations with the latest version of the NASA Ames Mars global climate model (GCM), gcm2.3+, that includes a modernized radiative-transfer package and complex water-ice cloud microphysics package which permit radiative effects and interactions of suspended atmospheric aerosols (e.g., water ice clouds, water vapor, dust, and mutual interactions) to influence the net diabatic heating. Results indicate that radiatively active water ice clouds profoundly affect the seasonal and annual mean climate. The mean thermal structure and balanced circulation patterns are strongly modified near the surface and aloft. Warming of the subtropical atmosphere at altitude and cooling of the high latitude atmosphere at low levels takes place, which increases the mean pole-to-equator temperature contrast (i.e., "baroclinicity"). With radiatively active water ice clouds (RAC) compared to radiatively inert water ice clouds (nonRAC), significant changes in the intensity of the mean state and forced stationary Rossby modes occur, both of which affect the vigor and intensity of traveling, synoptic period weather systems. Such weather systems not only act as key agents in the transport of heat and momentum beyond the extent of the Hadley circulation, but also the transport of trace species such as water vapor, water ice-clouds, dust and others. The northern hemisphere (NH) forced Rossby waves and resultant wave train are augmented in the RAC case: the modes are more intense and the wave train is shifted equatorward. Significant changes also occur within the subtropics and tropics. The Rossby wave train sets up, combined with the traveling synoptic-period weather systems (i.e., cyclones and anticyclones), the geographic extent of storm zones (or storm tracks) within the NH. A variety of circulation features will be presented which indicate contrasts between the RAC and nonRAC cases, and which highlight key effects radiatively-active clouds have on physical and dynamical processes active in the current climate of Mars.

NASA Ames Mars global climate model (GCM)↗

NASA NTRS1993

Analyzing Martian winds and tracer concentrations using Mars Observer data

During the courses of a day, the Mars Observer spacecraft will acquire globally distributed profiles of the martian atmosphere. It is highly desirable that this data be assembled into synoptic weather maps (complete specifications of the atmospheric pressure, temperature, and winds at a given time), which can in turn be used as starting points in the study of many meteorological phenomena. Unfortunately, the special nature of the Mars Observer data presents several challenges above and beyond the usual difficult problem of data initialization. Mars Observer atmospheric data will consist almost exclusively of asynoptic vertical profiles of temperatures (or radiances) and pressures, whereas winds are generally in balance with horizontal gradients of these quantities (which will not be observed). It will therefore be necessary to resort to dynamical models to analyze the wind fields. As a rule, data assimilation into atmospheric models can result in the generation of spurious gravity waves, so special steps must be taken to suppress these. In addition, the asynoptic nature of the data will require a four-dimensional (space and time) data assimilation scheme. The problem is to find a full set of meteorological fields (winds and temperatures) such that, when marched forward in time in the model, they achieve a best fit (in the weighted least-squares sense) to the data. The proposed solution is to develop a model especially for the Mars Observer data assimilation problem. Gravity waves are filtered from the model by eliminating all divergence terms from the prognostic divergence equation. This leaves a diagnostic gradient wind relation between the rotational wind and the temperature field. The divergent wind is diagnosed as the wind required to maintain the gradient wind balance in the presence of the diabatic heating. The primitive equations of atmospheric dynamics (with three principal dependent variables) are thus reduced to a simpler system with a single prognostic equation for temperature - the variable that will be best observed. (This balance system was apparently first derived by Charney as a first-order Rossby number expansion of the equations of motion). Experience with a full primitive equation model of the martian atmosphere indicates that a further simplification is possible: at least for short-term integrations, the model can be linearized about the zonally symmetric basic state.

Houben, Howard C.↗

DOE OSTI2023

A Practical Approach to Wave Function Propagation, Hopping Probabilities, and Time Steps in Surface Hopping Calculations

We compare several established approaches for propagating wave functions and calculating hopping probabilities within the fewest switches surface hopping (FSSH) algorithm for difficult cases with many electronic states and many trivial crossings. If only a single time step (Δt c ) is employed, we find that no published approach can accurately capture the dynamics correctly unless Δt c → 0 (which is not computationally feasible). If multiple time steps are employed, for a fixed classical time step (Δt c ), a robust scheme can be found for dynamically choosing quantum time steps (δt q1 and δt q2 ) and calculating hopping probabilities so that one can systematically reduce all errors and achieve maximally efficient accuracy; scattering calculations confirm that one can choose a fairly large classical time step. Furthermore, the robust scheme presented here uses both the “local diabatic” and adiabatic interpolation and thus borrows elements from both the Granucci/Persico and Meek/Levine algorithms. Our findings should be broadly applicable in the future.

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DOE OSTI2026

String-Breaking Dynamics in Quantum Adiabatic and Diabatic Processes

Confinement prohibits isolation of color charges, e.g., quarks, in nature via a process called string breaking : the separation of two charges results in an increase in the energy of a color flux, visualized as a string, connecting those charges. Eventually, creating additional charges is energetically favored, hence breaking the string. Such a phenomenon can be probed in simpler models, including quantum spin chains, enabling enhanced understanding of string-breaking dynamics. A challenging task is to understand how string breaking occurs as time elapses, in an out-of-equilibrium setting. This work establishes the phenomenology of dynamical string breaking induced by a gradual increase of string tension over time. It, thus, goes beyond instantaneous quench processes and enables tracking the real-time evolution of strings in a more controlled setting. We focus on domain-wall confinement in a family of quantum Ising chains. Our results indicate that, for sufficiently short strings and slow evolution, string breaking can be described by the transition dynamics of a two-state quantum system akin to a Landau-Zener process. For longer strings, a more intricate spatiotemporal pattern emerges: the string breaks by forming a superposition of bubbles (domains of flipped spins of varying sizes), which involve highly excited states. We finally demonstrate that string breaking driven only by quantum fluctuations can be realized in the presence of sufficiently long-ranged interactions. This work holds immediate relevance for studying string breaking in quantum-simulation experiments.

Ising model↗

NASA NTRS2003

Modeling, Simulation, and Forecasting of Subseasonal Variability

A planning workshop on "Modeling, Simulation and Forecasting of Subseasonal Variability" was held in June 2003. This workshop was the first of a number of meetings planned to follow the NASA-sponsored workshop entitled "Prospects For Improved Forecasts Of Weather And Short-Term Climate Variability On Sub-Seasonal Time Scales" that was held April 2002. The 2002 workshop highlighted a number of key sources of unrealized predictability on subseasonal time scales including tropical heating, soil wetness, the Madden Julian Oscillation (MJO) [a.k.a Intraseasonal Oscillation (ISO)], the Arctic Oscillation (AO) and the Pacific/North American (PNA) pattern. The overarching objective of the 2003 follow-up workshop was to proceed with a number of recommendations made from the 2002 workshop, as well as to set an agenda and collate efforts in the areas of modeling, simulation and forecasting intraseasonal and short-term climate variability. More specifically, the aims of the 2003 workshop were to: 1) develop a baseline of the "state of the art" in subseasonal prediction capabilities, 2) implement a program to carry out experimental subseasonal forecasts, and 3) develop strategies for tapping the above sources of predictability by focusing research, model development, and the development/acquisition of new observations on the subseasonal problem. The workshop was held over two days and was attended by over 80 scientists, modelers, forecasters and agency personnel. The agenda of the workshop focused on issues related to the MJO and tropicalextratropical interactions as they relate to the subseasonal simulation and prediction problem. This included the development of plans for a coordinated set of GCM hindcast experiments to assess current model subseasonal prediction capabilities and shortcomings, an emphasis on developing a strategy to rectify shortcomings associated with tropical intraseasonal variability, namely diabatic processes, and continuing the implementation of an experimental forecast and model development program that focuses on one of the key sources of untapped predictability, namely the MJO. The tangible outcomes of the meeting included: 1) the development of a recommended framework for a set of multi-year ensembles of 45-day hindcasts to be carried out by a number of GCMs so that they can be analyzed in regards to their representations of subseasonal variability, predictability and forecast skill, 2) an assessment of the present status of GCM representations of the MJO and recommendations for future steps to take in order to remedy the remaining shortcomings in these representations, and 3) a final implementation plan for a multi-institute/multi-nation Experimental MJO Prediction Program.

Waliser, Duane↗

NASA NTRS2000

GCSS Idealized Cirrus Model Comparison Project

The GCSS Working Group on Cirrus Cloud Systems (WG2) is conducting a systematic comparison and evaluation of cirrus cloud models. This fundamental activity seeks to support the improvement of models used for climate simulation and numerical weather prediction through assessment and improvement of the "process" models underlying parametric treatments of cirrus cloud processes in large-scale models. The WG2 Idealized Cirrus Model Comparison Project is an initial comparison of cirrus cloud simulations by a variety of cloud models for a series of idealized situations with relatively simple initial conditions and forcing. The models (16) represent the state-of-the-art and include 3-dimensional large eddy simulation (LES) models, two-dimensional cloud resolving models (CRMs), and single column model (SCM) versions of GCMs. The model microphysical components are similarly varied, ranging from single-moment bulk (relative humidity) schemes to fully size-resolved (bin) treatments where ice crystal growth is explicitly calculated. Radiative processes are included in the physics package of each model. The baseline simulations include "warm" and "cold" cirrus cases where cloud top initially occurs at about -47C and -66C, respectively. All simulations are for nighttime conditions (no solar radiation) where the cloud is generated in an ice supersaturated layer, about 1 km in depth, with an ice pseudoadiabatic thermal stratification (neutral). Continuing cloud formation is forced via an imposed diabatic cooling representing a 3 cm/s uplift over a 4-hour time span followed by a 2-hour dissipation stage with no cooling. Variations of these baseline cases include no-radiation and stable-thermal-stratification cases. Preliminary results indicated the great importance of ice crystal fallout in determining even the gross cloud characteristics, such as average vertically-integrated ice water path (IWP). Significant inter-model differences were found. Ice water fall speed is directly related to the shape of the particle size distribution and the habits of the ice crystal population, whether assumed or explicitly calculated. In order to isolate the fall speed effect from that of the associated ice crystal population, simulations were also performed where ice water fall speed was set to the same constant value everywhere in each model. Values of 20 and 60 cm/s were assumed. Current results of the project will be described and implications will be drawn. In particular, this exercise is found to strongly focus the definition of issues resulting in observed inter-model differences and to suggest possible strategies for observational validation of the models. The next step in this project is to perform similar comparisons for well observed case studies with sufficient high quality data to adequately define model initiation and forcing specifications and to support quantitative validation of the results.

Starr, David OC.↗

NASA NTRS2013

The Precipitation Response Over the Continental United States to Cold Tropical Pacific Sea Surface Temperatures

The dominant pattern of annual mean SST variability in the Pacific (in its cold phase) produces pronounced precipitation deficits over the continental United States (U.S.) throughout the annual cycle. This study investigates the physical and dynamical processes through which the cold Pacific pattern affects the U.S. precipitation, particularly the causes for the peak dry impacts in fall, as well as the nature of the differences between the summer and fall responses. Results, based on observations and reanalyses, show that the peak precipitation deficit over the U.S. during fall is primarily due to reduced atmospheric moisture transport from the Gulf of Mexico into the central and eastern U.S., and secondarily due to a reduction in local evaporation from land-atmosphere feedback. The former is associated with a strong and systematic low-level northeasterly flow anomaly over the southeastern U.S. that counteracts the northwest branch of the climatological flow associated with the north Atlantic subtropical high. The above northeasterly anomaly is maintained by both diabatic heating anomalies in the nearby Intra-American Seas and diabatic cooling anomalies in the tropical Pacific. In contrast, the modest summertime precipitation deficit over the U.S. is mainly the result of local land-atmosphere feedback; the rather weak and disorganized atmospheric circulation anomalies over and to the south of the U.S. make little contribution. An evaluation of NSIPP-1 AGCM simulations shows it to be deficient in simulating the warm season tropical convection responses over the Intra-American Seas to the cold Pacific pattern and thereby the precipitation responses over the U.S., a problem that appears to be common to many AGCMs.

SST↗

DOE OSTI2020

Real-Time Time-Dependent Nuclear–Electronic Orbital Approach: Dynamics beyond the Born–Oppenheimer Approximation

The quantum mechanical treatment of both electrons and nuclei is crucial in nona- diabatic dynamical processes such as proton-coupled electron transfer. The nuclear electronic orbital (NEO) method provides an elegant framework for including nuclear quantum effects beyond the Born-Oppenheimer approximation. To enable the study of nonequilibrium properties, we derive and implement a real-time NEO (RT-NEO) approach based on time-dependent Hatree-Fock or density functional theory, in which both the electronic and nuclear degrees of freedom are propagated in a time-dependent variational framework. Nuclear and electronic spectral features can be resolved from the time-dependent dipole moment computed using the RT-NEO method. The test cases demonstrate the dynamical interplay between the quantum nuclei and the electrons through vibronic coupling. Moreover, vibrational excitation in the RT-NEO approach is demonstrated by applying a resonant driving eld, and electronic excitation is demonstrated by simulating excited state intramolecular proton transfer. This work shows that the RT-NEO approach is a promising tool to study nonadiabatic quantum dynamical processes within a time-dependent variational description for the coupled electronic and nuclear degrees of freedom.

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