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At least 1,117 records · Page 62
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Effects of ion adsorption on graphene oxide films and interfacial water structure: A molecular-scale description

Herein we discuss graphene oxide as a promising, emerging separation material, as it is durable, dispersible in water, and has naturally forming functional groups. Bulk studies using graphene oxide flakes have demonstrated impressive metal adsorption. However, little interfacial information about water and metal organization near graphene oxide is available. A mechanistic understanding of water and ions interactions with graphene oxide films is critical toward advanced separations, including improved sorption efficiency and membrane regeneration. We study metal ion and local water organization near graphene oxide thin films formed at the air/water interface. These films are not typical membranes and allow us to determine nanoscale information about the graphene oxide-water interface. We accomplish this with x-ray reflectivity (XR), x-ray fluorescence near total reflection (XFNTR), and vibrational sum frequency generation spectroscopy (SFG). These interface-specific techniques provide the electron density profile normal to the interface, number of adsorbed ions, and information about the orientational ordering and hydrogen-bonding network of interfacial water, respectively. Via XFNTR and SFG, we find that trivalent yttrium ions preferentially adsorb to graphene oxide and affect its structure, compared to divalent strontium and monovalent cesium ions. Two different interfacial water populations can be described, based on their hydrogen bonding strength, and the adsorbed ions affect these populations differently. These results provide fundamental information about ion and water organization at the interface and help address the large computational-experimental agreement gap for graphene oxide systems. Additionally, they are relevant for improved soft-scaffold graphene oxide membranes and downstream applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Completely Multipolar Model for Many-Body Water–Ion and Ion–Ion Interactions

This work constructs an advanced force field, the Completely Multipolar Model (CMM), to quantitatively reproduce each term of an energy decomposition analysis (EDA) for aqueous solvated alkali metal cations and halide anions and their ion pairings. We find that all individual EDA terms remain well-approximated in the CMM for ion-water and ion-ion interactions, except for polarization, which shows errors due to the partial covalency of ion interactions near their equilibrium. We quantify the onset of the dative bonding regime by examining the change in molecular polarizability and Mayer bond indices as a function of distance, showing that partial covalency manifests by breaking the symmetry of atomic polarizabilities while strongly damping them at short-range. This motivates an environment-dependent atomic polarizability parameter that depends on the strength of the local electric field experienced by the ions to account for strong damping, with anisotropy introduced by atomic multipoles. The resulting CMM model for ions provides accurate dimer surfaces and three-body polarization and charge transfer compared to EDA, and shows excellent performance on various ion benchmarks including vibrational frequencies and cluster geometries.

Heindel, Joseph P↗
NASA NTRS1993

Hypersonic panel flutter in a rarefied atmosphere

Panel flutter is a form of dynamic aeroelastic instability resulting from the interaction between motion of an aircraft structural panel and the aerodynamic loads exerted on that panel by air flowing past one of the faces. It differs from lifting surface flutter in the sense that it is not usually catastrophic, the panel's motion being limited by nonlinear membrane stresses produced by the transverse displacement. Above some critical airflow condition, the linear instability grows to a limit cycle . The present investigation studies panel flutter in an aerodynamic regime known as 'free molecule flow', wherein intermolecular collisions can be neglected and loads are caused by interactions between individual molecules and the bounding surface. After collision with the panel, molecules may be reflected specularly or reemitted in diffuse fashion. Two parameters characterize this process: the 'momentum accommodation coefficient', which is the fraction of the specularly reflected molecules; and the ratio between the panel temperature and that of the free airstream. This model is relevant to the case of hypersonic flight vehicles traveling at very high altitudes and especially for panels oriented parallel to the airstream or in the vehicle's lee. Under these conditions the aerodynamic shear stress turns out to be considerably larger than the surface pressures, and shear effects must be included in the model. This is accomplished by means of distributed longitudinal and bending loads. The former can cause the panel to buckle. In the example of a simply-supported panel, it turns out that the second mode of free vibration tends to dominate the flutter solution, which is carried out by a Galerkin analysis. Several parametric studies are presented. They include the effects of (1) temperature ratio; (2) momentum accommodation coefficient; (3) spring parameters, which are associated with how the panel is connected to adjacent structures; (4) a parameter which relates compressive end load to its value which would cause classical column buckling; (5) a parameter proportional to the pressure differential between the front and back faces; and (6) initial curvature. The research is completed by an investigation into the possibility of accounting for molecular collisions, which proves to be infeasible given the speeds of current mainframe supercomputers.

Resende, Hugo B.↗
DOE OSTI2026

Isolating solvent–solute hydrogen bonding interactions via 2D IR solvation shell spectroscopy

The solvation shell around a solute is a fundamental feature of liquid-phase solutions, determining the behavior and properties of both the solute and the overall solution. Direct experimental measurements of the solvation shell properties are challenging due to the strong signals generated from the bulk solvent, which overwhelm the small contribution of the solvation shell. Here, we use ultrafast two dimensional infrared (2D IR) spectroscopy and intermolecular cross-peaks to isolate the IR absorption spectrum of methanol molecules in the solvation shell surrounding the solute N-methylacetamide. We demonstrate that the intermolecular coupling between the solvent and solute vibrations is indirectly mediated by a low-frequency hydrogen-bonding mode, suggesting an important mechanism for anharmonic coupling induced by hydrogen bonds. From the relative frequency shifts and cross-peak anisotropy, we find that methanol molecules surrounding N-methylacetamide form stronger and distinctly oriented hydrogen bonds than those in the bulk solvent. Here, we also compare these results with the solvent spectra of the solute N,N-dimethylacetamide to investigate how solute structural changes alter the solvation shell and the contribution of N–H hydrogen bond donation. Our results are supported by molecular dynamics simulations, which provide detailed insights into the hydrogen-bonding distributions. Through these results, we demonstrate 2D solvation shell spectroscopy to be a valuable method for investigating solvation structures and dynamics without interference from the bulk solvent.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Solvated Ionic Liquid-based Electrolytes: Experimental Characterization, Atomistic Modeling and Applications in Energy Storage

This study aimed on understanding the molecular structure and transport mechanisms of high-concentration lithium electrolytes, with a particular focus on solvate ionic liquids (SILs) based on glyme solvents, for use in next-generation, high-voltage energy storage systems. The hypothesis is that the composition of the solvents in these electrolytes can be designed and adjusted to control cation solvation, enabling charge transport via an ion-hopping mechanism. This mechanism resembles Grotthuss conduction of protons in water and is independent of electrolyte viscosity. The experimental studies employed linear and nonlinear infrared spectroscopy (FTIR and 2D IR), electrochemical measurements, and vibrational probes.

25 ENERGY STORAGE↗
NASA NTRS1986

Ultrasensitive detection of atmospheric trace gases using frequency modulation spectroscopy

Frequency modulation (FM) spectroscopy is a new technique that promises to significantly extend the state-of-the-art in point detection of atmospheric trace gases. FM spectroscopy is essentially a balanced bridge optical heterodyne approach in which a small optical absorption or dispersion from an atomic or molecular species of interest generates an easily detected radio frequency (RF) signal. This signal can be monitored using standard RF signal processing techniques and is, in principle, limited only by the shot noise generated in the photodetector by the laser source employed. The use of very high modulation frequencies which exceed the spectral width of the probed absorption line distinguishes this technique from the well-known derivative spectroscopy which makes use of low (kHz) modulation frequencies. FM spectroscopy was recently extended to the 10 micron infrared (IR) spectral region where numerous polyatomic molecules exhibit characteristic vibrational-rotational bands. In conjunction with tunable semiconductor diode lasers, the quantum-noise-limited sensitivity of the technique should allow for the detection of absorptions as small as .00000001 in the IR spectral region. This sensitivity would allow for the detection of H2O2 at concentrations as low as 1 pptv with an integration time of 10 seconds.

Cooper, David E.↗
DOE OSTI2022

Observation of Core-Excited Dipole-Bound States

Polar molecules can bind an electron in a diffuse orbital due to the charge-dipole interaction. Electronic excited states of polar molecules can also bind an electron to form core-excited dipole-bound states (DBSs), analogous to core-excited Rydberg states. However, core-excited DBSs have not been observed because of the complicated electronic structure of molecular systems. Here we report the observation of a core-excited DBS in the pyrazolide anion as a result of the favorable electronic structure of the neutral pyrazolyl core, which has a low-lying excited state ($\tilde{A}$ 2 B 1 ) only 266 cm -1 above its ground state ($\tilde{X}$ 2 A 2 ). The binding energy of the DBS associated with the ground state is measured to be 221 cm -1 , while that of the core-excited DBS is 276 cm -1 , which is still a bound state relative to the detachment threshold. Furthermore, vibrational Feshbach resonances are observed for both DBSs and their autodetachment behaviors are studied by resonant photoelectron imaging.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Spin-orbital coupling and slow phonon effects enabled persistent photoluminescence in organic crystal under isomer doping

When periodically packing the intramolecular donor-acceptor structures to form ferroelectric-like lattice identified by second harmonic generation, our CD49 molecular crystal shows long-wavelength persistent photoluminescence peaked at 542 nm with the lifetime of 0.43 s, in addition to the short-wavelength prompt photoluminescence peaked at 363 nm with the lifetime of 0.45 ns. Interestingly, the long-wavelength persistent photoluminescence demonstrates magnetic field effects, showing as crystalline intermolecular charge-transfer excitons with singlet spin characteristics formed within ferroelectric-like lattice based on internal minority/majority carrier-balancing mechanism activated by isomer doping effects towards increasing electron-hole pairing probability. Our photoinduced Raman spectroscopy reveals the unusual slow relaxation of photoexcited lattice vibrations, indicating slow phonon effects occurring in ferroelectric-like lattice. Here, we show that crystalline intermolecular charge-transfer excitons are interacted with ferroelectric-like lattice, leading to exciton-lattice coupling within periodically packed intramolecular donor-acceptor structures to evolve ultralong-lived crystalline light-emitting states through slow phonon effects in ferroelectric light-emitting organic crystal.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Structure determination of ζ-N 2 from single-crystal X-ray diffraction and theoretical suggestion for the formation of amorphous nitrogen

The allotropy of solid molecular nitrogen is the consequence of a complex interplay between fundamental intermolecular as well as intramolecular interactions. Understanding the underlying physical mechanisms hinges on knowledge of the crystal structures of these molecular phases. That is especially true for ζ-N 2 , key to shed light on nitrogen’s polymerization. Here, we perform single-crystal X-ray diffraction on laser-heated N 2 samples at 54, 63, 70 and 86 GPa and solve and refine the hitherto unknown structure of ζ-N 2 . In its monoclinic unit cell (space group C 2/ c ), 16 N 2 molecules are arranged in a configuration similar to that of ε-N 2 . The structure model provides an explanation for the previously identified Raman and infrared lattice and vibrational modes of ζ-N 2 . Density functional theory calculations give an insight into the gradual delocalization of electronic density from intramolecular bonds to intermolecular space and suggest a possible pathway towards nitrogen’s polymerization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1983

Intensity and extinction irregularities in the H2 emission from Orion

Fourteen lines of the v = 1-0 and v = 2-1 2 micron H2 quadrupole spectrum were measured in a series of ground-based spectroscopic observations of four locations within the Orion molecular cloud-H2 emission complex. Beam sizes of 7 and 10 arcsec were used, with a resolution of 1.8/cm. The results indicate that there are differences in the extinction between regions of as much as 20 mag. In particular there appears to be a ridge of material near the object IRS 2 (= IRc 9), a previously suggested source of activity. The 2-1 S (3) line intensity is substantially stronger at Peak 2 than the present models predict, and this observation is the first indication that there may be a non-Boltzmann distribution within the vibrational levels of shock-excited H2. A detection of the 1-0 Q (6) line is also reported, a feature which was previously absent in spectra of the Orion cloud.

Smith, H. A.↗
NASA NTRS1984

4.6 micron absorption features due to solid phase CO and cyano group molecules toward compact infrared sources

Spectra obtained at a resolving power of 840, for seven protostellar sources in the region of the 4.67-micron fundamental vibrational band of CO, indicate that the deep absorption feature in W33A near 4.61 microns consists of three features which are seen in other sources, but with varying relative strength. UV-irradiation laboratory experiments with 'dirty ice' temperature cycling allow the identification of two of the features cited with solid CO and CO complexed to other molecules. Cyano group-containing molecules have a lower vapor pressure than CO, and can therefore survive in much warmer environments. The formation and location of the CO- and CN-bearing grain mantles and sources of UV irradiation in cold molecular clouds are discussed. Plausible UV light sources can produce the observed cyano group features, but only under conditions in which local heat sources do not cause evaporation of the CO molecules prior to their photoprocessing.

Lacy, J. H.↗
NASA NTRS1994

Electronic spectroscopy of diatomic molecules

This article provides an overview of the principal computational approaches and their accuracy for the study of electronic spectroscopy of diatomic molecules. We include a number of examples from our work that illustrate the range of application. We show how full configuration interaction benchmark calculations were instrumental in improving the understanding of the computational requirements for obtaining accurate results for diatomic spectroscopy. With this understanding it is now possible to compute radiative lifetimes accurate to within 10% for systems involving first- and second-row atoms. We consider the determination of the infrared vibrational transition probabilities for the ground states of SiO and NO, based on a globally accurate dipole moment function. We show how we were able to assign the a(sup "5)II state of CO as the upper state in the recently observed emission bands of CO in an Ar matrix. We next discuss the assignment of the photoelectron detachment spectra of NO and the alkali oxide negative ions. We then present several examples illustrating the state-of-the-art in determining radiative lifetimes for valence-valence and valence-Rydberg transitions. We next compare the molecular spectroscopy of the valence isoelectronic B2, Al2, and AlB molecules. The final examples consider systems involving transition metal atoms, which illustrate the difficulty in describing states with different numbers of d electrons.

Partridge, Harry↗
NASA NTRS2018

ALMA Spectral Line and Imaging Survey of a Low and a High Mass-Loss Rate AGB Star Between 335 and 362 GHz

Context. Low and intermediate mass stars are known to power strong stellar winds when evolving through the asymptotic giant branch (AGB) phase. Initial mass, luminosity, temperature, and composition determine the pulsation characteristics of the star and the dust species formed in the pulsating photospheric layers. Radiation pressure on these grains triggers the onset of a stellar wind. However, as of today, we still cannot predict the wind mass-loss rates and wind velocities from first principles neither do we know which species are the first to condense in the upper atmospheric regions. Aims. We aim to characterise the dominant physical, dynamical, and chemical processes in the inner wind region of two archetypical oxygen-rich (C/O<1) AGB stars, that is, the low mass-loss rate AGB star R Dor (M~ 1x10(exp 7) M☉/yr) and the high mass-loss rate AGB star IK Tau (M~5x10(exp 6) M☉/yr). The purpose of this study is to observe the key molecular species contributing to the formation of dust grains and to cross-link the observed line brightnesses of several species to the global and local properties of the star and its wind. Methods. A spectral line and imaging survey of IK Tau and R Dor was made with ALMA between 335 and 362 GHz (band 7) at a spatial resolution of ~150 mas, which corresponds to the locus of the main dust formation region of both targets. Results. Some two hundred spectral features from 15 molecules (and their isotopologues) were observed, including rotational lines in both the ground and vibrationally excited states (up to v=5 for SiO). Detected species include the gaseous precursors of dust grains such as SiO, AlO, AlOH, TiO, and TiO2.We present a spectral atlas for both stars and the parameters of all detected spectral features. A clear dichotomy for the sulphur chemistry is seen: while CS, SiS, SO, and SO2 are abundantly present in IK Tau, only SO and SO2 are detected in R Dor. Also other species such as NaCl, NS, AlO, and AlOH display a completely different behaviour. From some selected species, the minor isotopologues can be used to assess the isotopic ratios. The channel maps of many species prove that both large and small-scale inhomogeneities persist in the inner wind of both stars in the form of blobs, arcs, and/or a disk. The high sensitivity of ALMA allows us to spot the impact of these correlated density structures in the spectral line profiles. The spectral lines often display a half width at zero intensity much larger than expected from the terminal velocity, v1, previously derived for both objects (36 km/s versus v(∞)~17.7 km/s for IK Tau and 23 km/s versus v(∞)~5.5 km/s for R Dor). Both a more complex 3D morphology and a more forceful wind acceleration of the (underlying) isotropic wind can explain this trend. The formation of fractal grains in the region beyond _400 mas can potentially account for the latter scenario. From the continuum map, we deduce a dust mass of ~3.7 x 10(exp 7) M☉ and ~2 x 10(ex0 8) M☉ for IK Tau and R Dor, respectively. Conclusions. The observations presented here provide important constraints on the properties of these two oxygen-dominated AGB stellar winds. In particular, the ALMA data prove that both the dynamical and chemical properties are vastly different for this high mass-loss rate (IK Tau) and low mass-loss rate (R Dor) star.

Stars: AGB and post-AGB, Stars: mass loss, Stars: ↗
NASA NTRS2018

ALMA Spectral Line and Imaging Survey of a Low and a High Mass-Loss Rate AGB Star Between 335 and 362 GHz

Context. Low and intermediate mass stars are known to power strong stellar winds when evolving through the asymptotic giant branch (AGB) phase. Initial mass, luminosity, temperature, and composition determine the pulsation characteristics of the star and the dust species formed in the pulsating photospheric layers. Radiation pressure on these grains triggers the onset of a stellar wind. However, as of today, we still cannot predict the wind mass-loss rates and wind velocities from first principles neither do we know which species are the first to condense in the upper atmospheric regions. Aims. We aim to characterise the dominant physical, dynamical, and chemical processes in the inner wind region of two archetypical oxygen-rich (C/O < 1) AGB stars, that is, the low mass-loss rate AGB star R Dor (M’ ∼ 1 × 10(exp −7) M/yr) and the high mass-loss rate AGB star IK Tau (M’ ∼ 5 × 10(exp −6) M/yr). The purpose of this study is to observe the key molecular species contributing to the formation of dust grains and to cross-link the observed line brightnesses of several species to the global and local properties of the star and its wind. Methods. A spectral line and imaging survey of IK Tau and R Dor was made with ALMA between 335 and 362 GHz (band 7) at a spatial resolution of ∼150 mas, which corresponds to the locus of the main dust formation region of both targets. Results. Some two hundred spectral features from 15 molecules (and their isotopologues) were observed, including rotational lines in both the ground and vibrationally excited states (up to v = 5 for SiO). Detected species include the gaseous precursors of dust grains such as SiO, AlO, AlOH, TiO, and TiO2. We present a spectral atlas for both stars and the parameters of all detected spectral features. A clear dichotomy for the sulphur chemistry is seen: while CS, SiS, SO, and SO2 are abundantly present in IK Tau, only SO and SO2 are detected in R Dor. Also other species such as NaCl, NS, AlO, and AlOH display a completely different behaviour. From some selected species, the minor isotopologues can be used to assess the isotopic ratios. The channel maps of many species prove that both large and small-scale inhomogeneities persist in the inner wind of both stars in the form of blobs, arcs, and/or a disk. The high sensitivity of ALMA allows us to spot the impact of these correlated density structures in the spectral line profiles. The spectral lines often display a half width at zero intensity much larger than expected from the terminal velocity, v∞, previously derived for both objects (36 km/s versus v(∞) ∼ 17.7 km/s for IK Tau and 23 km/s versus v(∞) ∼ 5.5 km/s for R Dor). Both a more complex 3D morphology and a more forceful wind acceleration of the (underlying) isotropic wind can explain this trend. The formation of fractal grains in the region beyond ∼400 mas can potentially account for the latter scenario. From the continuum map, we deduce a dust mass of ∼3.7 × 10(exp −7) Mand ∼2 × 10(exp −8) M for IK Tau and R Dor, respectively. Conclusions. The observations presented here provide important constraints on the properties of these two oxygen-dominated AGB stellar winds. In particular, the ALMA data prove that both the dynamical and chemical properties are vastly different for this high mass-loss rate (IK Tau) and low mass-loss rate (R Dor) star.

L. Decin↗
DOE OSTI2026

Photodissociation and Infrared Spectroscopy of U + (CO 2 ) n , UO + (CO 2 ) n , and UO 2+ (CO 2 ) n Cation-Molecular Complexes

Laser vaporization of uranium in a pulsed supersonic expansion of carbon dioxide is used to produce complexes of the form U + (CO 2 ) n , UO + (CO 2 ) n , and UO 2+ (CO 2 ) n . These ions are selected in a reflectron time-offlight mass spectrometer and studied with visible laser photodissociation and tunable infrared laser photodissociation spectroscopy in the region of the CO 2 antisymmetric stretch. The dissociation patterns and spectroscopy of these ions indicate that CO 2 ligands are intact molecules. Although reaction products that form oxide-carbonyl or oxalate species are predicted to be stable, there is no direct evidence in the frequency range studied for the formation of these species. There is no clear indication for the coordination numbers for singly charged uranium and its oxide complexes with CO 2 . However, there is strong support in the vibrational patterns for an eight-coordinate complex of the doubly charged UO 2+ species, i.e., UO 2+ (CO 2 ) 8 .

Cluster chemistry↗
NASA NTRS2004

Vibrational Spectroscopy at Cryogenic Temperatures: From the Laboratory to the Ends of the Universe

Polycyclic aromatic compounds (PAC) have been the subject of astrophysical interest for nearly two decades. Indeed, there is now evidence that these compounds are among the most abundant interstellar molecules, comprising perhaps 10 - 30% of all the carbon in our galaxy. Ranging in size from as few as 20 to as many as hundreds or thousands of carbon atoms, these molecules are enormous by interstellar standards and impact a wide range of astrophysical phenomena including: the near- and mid-infrared emission spectrum of a wide range of astronomical objects; the ultraviolet/visible/near-infrared absorption of the diffuse medium that permeates our galaxy; and the heating and cooling mechanisms of interstellar clouds. Nevertheless, until recently a lack of laboratory spectroscopic data on PAC under astrophysically relevant conditions (i.e. isolated, ionized molecules; ionized molecular clusters, etc.) has hindered critical evaluation and extension of this model. Fortunately, the last decade has seen an explosion of experimental and theoretical techniques aimed specifically at addressing these issues. Here, we begin with a brief review of the evidence for the existence and abundance of interstellar PAC. From there, we move on to an overview of the general spectroscopic characteristics of the range of isolated, neutral and ionized PAC that we have studied over the last decade. Finally, we will conclude with a consideration of the astrophysical implications and applications of interstellar PAC. Our discussion will revolve primarily around the observed interstellar infrared emission spectra and the ability of the laboratory spectra of varying combinations of PAC to accommodate both the global appearance and the region-to-region variability of this emission. Careful models based on sound laboratory spectroscopic data such as these now have the potential to provide insight into the structure, abundance, and ionization state of the interstellar PAC population. That, in turn, will provide direct insight into the processes of carbon nucleation, growth and evolution as matter is processed through the interstellar medium.

Hudgins, Douglas M.↗
DOE OSTI2024

The Role of Spin–Orbit Coupling in the Linear Absorption Spectrum and Intersystem Crossing Rate Coefficients of Ruthenium Polypyridyl Dyes

The successful use of molecular dyes for solar energy conversion requires efficient charge injection, which in turn requires the formation of states with sufficiently long lifetimes (e.g., triplets). The molecular structure elements that confer this property can be found empirically, however computational predictions using ab initio electronic structure methods are invaluable to identify structure-property relations for dye sensitizers. The primary challenge for simulations to elucidate the electronic and nuclear origins of these properties is a spin-orbit interaction which drives transitions between electronic states. Here, in this work, we present a computational analysis of the spin-orbit corrected linear absorption cross sections and intersystem crossing rate coefficients for a derivative set of phosphonated tris(2,2'-bipyridine)ruthenium(2+) dye molecules. After sampling the ground state vibrational distributions, the predicted linear absorption cross sections indicate that the mixture between singlet and triplet states plays a crucial role in defining the line shape of the metal-to-ligand charge transfer bands in these derivatives. Additionally, an analysis of the intersystem crossing rate coefficients suggests that transitions from the singlet into the triplet manifolds are ultrafast with rate coefficients on the order of 10 13 s -1 for each dye molecule.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Fermi’s Golden Rule Rate Expression for Transitions Due to Nonadiabatic Derivative Couplings in the Adiabatic Basis

Starting from a general molecular Hamiltonian expressed in the basis of adiabatic electronic and nuclear position states, where a compact and complete expression for the nonadiabatic derivative coupling (NDC) Hamiltonian term is obtained, we provide a general analysis of the Fermi’s golden rule (FGR) rate expression for nonadiabatic transitions between adiabatic states. We then consider a quasi-adiabatic approximation that uses crude adiabatic states and NDC couplings, both evaluated at the minimum potential energy configuration of the initial adiabatic state, for the definition of the zeroth and first-order terms of the Hamiltonian. Although the application of this approximation is rather limited, it allows deriving a general FGR rate expression without further approximation while accounting for non-Condon contribution to the FGR rate arising from momentum operators of NDC terms and its coupling with vibronic displacements. For a generic and widely used model where all nuclear degrees of freedom and environmental effects are represented as linearly coupled harmonic oscillators, we derive a closed-form FGR rate expression that requires only Fourier transform. The resulting rate expression includes quadratic contributions of NDC terms and their couplings to Franck–Condon modes, which require evaluation of two additional bath spectral densities in addition to the conventional one that appears in a typical FGR rate theory based on the Condon approximation. Model calculations for the case where nuclear vibrations consist of both a sharp high-frequency mode and an Ohmic bath spectral density illustrate new features and implications of the rate expression. We then apply our theoretical expression to the nonradiative decay from the first excited singlet state of azulene, which illustrates the utility and implications of our theoretical results.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗