Electronic Potential Energy Surfaces Research Articles

Dynamic interpretation of resonant x-ray Raman scattering: Ethylene and benzene

We present a dynamic interpretation of resonant x-ray Raman scattering where vibrationally selective excitation into molecular resonances has been employed in comparison with excitation into higher lying continuum states for condensed ethylene and benzene as molecular model systems. In order to describe the purely vibrational spectral loss features and coupled electronic and vibrational losses the one-step theory for resonant soft x-ray scattering is applied, taking multiple vibrational modes and vibronic coupling into account. The scattering profile is found to be strongly excitation energy dependent and to reflect the intermediate states dynamics of the scattering process. In particular, the purely vibrational loss features allow one to map the electronic ground state potential energy surface in light of the excited state dynamics. Our study of ethylene and benzene underlines the necessity of an explicit description of the coupled electronic and vibrational loss features for the assignment of spectral features observed in resonant x-ray Raman scattering at polyatomic systems, which can be done in both a time independent and a time dependent picture. The possibility to probe ground state vibrational properties opens a perspective to future applications of this photon-in-photon-out spectroscopy.

Adiabatic Passage in a Three-State System with Non-Markovian Relaxation: The Role of Excited-State Absorption and Two-Exciton Processes

The influence of excited-state absorption (ESA) and two-exciton processes on a coherent population transfer with intense ultrashort chirped pulses in molecular systems in solution has been studied. A unified treatment of adiabatic rapid passage (ARP) in such systems has been developed using a three-state electronic system with relaxation treated as a diffusion on electronic potential energy surfaces. We have shown that ESA has a profound effect on coherent population transfer in large molecules that necessitates a more accurate interpretation of experimental data. A simple and physically clear model for ARP in molecules with three electronic states in solution has been developed by extending the Landau-Zener calculations putting in a third level to random crossing of levels. A method for quantum control of two-exciton states in molecular complexes has been proposed.

Semiclassical nonadiabatic dynamics of NaFH with quantum trajectories

The semiclassical quantum trajectory method is applied to a large-gap (∼1 eV) nonadiabatic system, NaFH van der Waals complex treated in two dimensions. Single surface quantum effects on the FH fragment including the quasibound state decay are described using the approximate quantum potential method. Trajectory dynamics unfolds on a superposition of the electronic potential energy surfaces weighted by the surface populations. Transfer of wavefunctions between the surfaces is described by means of the population amplitude prefactors. Approximate quantum trajectory dynamics gives qualitative agreement with exact results which improves in the semiclassical regime of reduced coupling strength.

A simple density functional fractional occupation number procedure to determine the low energy transition region of spin-flip reactions

A computationally simple three-step procedure to survey the energy landscape and to determine the molecular transition structure and activation energy at the intersection of two weakly coupled electronic potential energy surfaces of different symmetry is suggested. Only commercial software is needed to obtain the transition states of, for instance, spin-flip reactions. The computational expense is only two to three times larger than that of the standard determination of an adiabatic reaction path. First, the structures of the two electronic initial and final states along a chosen reaction coordinate are individually optimized. At the "projected crossing," the two states have the same energy at the same value of the reaction coordinate, but different state-optimized partial structures. Second, the unique optimized structure of a low energy crossing point between the two states is determined with the help of the density functional fractional occupation number approach. Finally, the respective energy of the two states at the crossing is estimated by a single point calculation. The prescription is successfully applied to some simple topical examples from organic and from inorganic chemistry, respectively, concerning the spin-flip reactions (3)H(3)CS(+)-->(1)H(2)CSH(+) and (7)MoCO(2)-->(5)MoCO(2)-->(3)OMoCO.

Large scale vibrational Hamiltonian calculations on thiophosgene

The vibrational spectrum and ground electronic state potential energy surface (PES) of thiophosgene (CSCl 2) have been studied quantum mechanically using a completely symmetrized Hamiltonian formalism and vibrational basis set, including all six molecular vibrational modes in the calculations. The calculated vibrational frequencies have been compared to the experimentally measured data by other authors. From a good fit achieved between the theoretical and experimental frequencies up to considerably high excess vibrational energies, the harmonic and some anharmonic (cubic and quartic) force constants of the molecular PES have been reliably determined.

Reactions of CF3CH2I+O(P3): Competing mechanisms of HF elimination

Ab initio density functional and molecular orbital calculations provide singlet and triplet electronic potential energy surfaces for the reactions of CF3CH2I+O(3P) leading to OI and HF eliminations, reactions which have been the subject of recent experimental studies. A barrier to OI formation occurs on the triplet potential energy surface; there is no reverse barrier to OI formation on the singlet pathway. Findings suggest that two competing pathways may form HF. One is an addition-insertion-elimination process involving insertion of O into the C-I bond. The alternate path involves OI elimination, addition of an O atom to CF3CH2, and subsequent HF elimination. The computed reactant pathways and energetics are discussed in relation to recent experiments.

Ultracold Rydberg atoms in a magneto-electric trap

We investigate the quantum properties of an ultracold Rydberg atom exposed to a magnetic quadrupole field and a homogeneous electric field. The properly transformed Hamiltonian explicitly depends on the conserved total angular momentum and couples the centre of mass and electronic degrees of freedom. The corresponding Schrödinger equation is solved by an adiabatic separation focusing on a fixed n-manifold. The shape of the adiabatic electronic potential energy surfaces is analysed. With increasing electric field strength, avoided crossings among them become ubiquitous and the electric field-dominated regime spreads out within the centre-of-mass coordinate space. A transition from smooth surfaces for weak electric fields to surfaces involving a cusp-like behaviour in the strong field regime is observed. The latter involves a characteristic splitting behaviour of the surfaces due to the competition of the Stark and magnetic interactions. In contrast to previous investigations, our setup allows for the trapping of quantum states with a comparatively small electronic angular momentum.

Modeling Deoxyribonucleic Acid and Ribonucleic Acid Damage in the Gas Phase

This short review outlines the tandem mass spectrometric methods for the generation and analysis of transient nucleobase radicals relevant to deoxyribonucleic acid and ribonucleic acid damage. Radical hydrogen atom adducts to uracil, adenine, cytosine and N-methylcytosine were generated by femtosecond electron transfer to the corresponding gas-phase cations in fast beams at 8 keV kinetic energy. Radical unimolecular dissociations were monitored by product analysis following collisional ionization to cations or anions using neutralization-reionization mass spectrometry. The radical energetics and dissociation kinetics were further analyzed by mapping the potential energy surfaces by high-level ab initio calculations in combination with Rice-Remsberger-Kassel-Marcus calculations of unimolecular rate constants. This first- principles-based approach allows one to model radical dissociations occurring from doublet ground electronic states of radical intermediates, assign reaction mechanisms and derive quantitative branching ratios for dissociation channels that are in agreement with experiments. Theoretical analysis also provides distinction between radical dissociations occurring on the ground and excited electronic state potential energy surfaces. Specific characterization of excited state dissociations of nucleobase and other polyatomic radicals remains a challenging topic for both experimentalists and computational chemists.

The Nearly Degenerate Triplet Electronic Ground State Isomers of Lithium Nitroxide

The triplet electronic ground state potential energy surface of lithium nitroxide has been systematically investigated using convergent quantum mechanical methods. Equilibrium structures and physical properties for five stationary points (three minima and two transition states) have been determined employing highly correlated coupled cluster theory with four correlation-consistent polarized-valence (cc-pVXZ and aug-cc-pVXZ, X = T and Q) and two core correlation-consistent polarized-valence (cc-pCVXZ, X = T and Q) basis sets. The global minimum, roughly L-shaped Li-O-N, is predicted to lie 6.5 kcal mol-1 below the linear LiON minimum and 2.4 kcal mol-1 below the linear LiON minimum. The barrier to isomerization from the global minimum to LiON was found to be 7.4 kcal mol-1 and with regard to LiNO 6.9 kcal mol-1. The dissociation energies, D0, with respect to Li + NO, have been predicted for all minima and for the global minimum was found to be 34.9 kcal mol-1.

Inelastic scattering matrix elements for the nonadiabatic collision B(P1∕22)+H2(Σg+1,j)↔B(P3∕22)+H2(Σg+1,j′)

Inelastic scattering matrix elements for the nonadiabatic collision B(P1∕22)+H2(Σg+1,j)↔B(P3∕22)+H2(Σg+1,j′) are calculated using the time dependent channel packet method (CPM). The calculation employs 1A′2, 2A′2, and 1A″2 adiabatic electronic potential energy surfaces determined by numerical computation at the multireference configuration-interaction level [M. H. Alexander, J. Chem. Phys. 99, 6041 (1993)]. The 1A′2 and 2A′2, adiabatic electronic potential energy surfaces are transformed to yield diabatic electronic potential energy surfaces that, when combined with the total B+H2 rotational kinetic energy, yield a set of effective potential energy surfaces [M. H. Alexander et al., J. Chem. Phys. 103, 7956 (1995)]. Within the framework of the CPM, the number of effective potential energy surfaces used for the scattering matrix calculation is then determined by the size of the angular momentum basis used as a representation. Twenty basis vectors are employed for these calculations, and the corresponding effective potential energy surfaces are identified in the asymptotic limit by the H2 rotor quantum numbers j=0, 2, 4, 6 and B electronic states Pja2, ja=1∕2, 3∕2. Scattering matrix elements are obtained from the Fourier transform of the correlation function between channel packets evolving in time on these effective potential energy surfaces. For these calculations the H2 bond length is constrained to a constant value of req=1.402a.u. and state to state scattering matrix elements corresponding to a total angular momentum of J=1∕2 are discussed for j=0↔j′=0,2,4 and P1∕22↔P1∕22, P3∕22 over a range of total energy between 0.0 and 0.01a.u.

Isomerization dynamics and thermodynamics of ionic argon clusters

The dynamics and thermodynamics of small Ar(n) (+) clusters, n=3, 6, and 9, are investigated using molecular dynamics (MD) and exchange Monte Carlo (MC) simulations. A diatomic-in-molecule Hamiltonian provides an accurate model for the electronic ground state potential energy surface. The microcanonical caloric curves calculated from MD and MC methods are shown to agree with each other, provided that the rigorous conservation of angular momentum is accounted for in the phase space density of the MC simulations. The previously proposed projective partition of the kinetic energy is used to assist MD simulations in interpreting the cluster dynamics in terms of inertial, internal, and external modes. The thermal behavior is correlated with the nature of the charged core in the cluster by computing a dedicated charge localization order parameter. We also perform systematic quenches to establish a connection with the various isomers. We find that the Ar(3) (+) cluster is very stable in its linear ground state geometry up to about 300 K, and then isomerizes to a T-shaped isomer in which a quasineutral atom lies around a charged dimer. In Ar(6) (+) and Ar(9) (+), the covalent trimer core is solvated by neutral atoms, and the weakly bound solvent shell melts at much lower energies, occasionally leading to a tetramer or pentamer core with weakly charged extremities. At high energies the core itself becomes metastable and the cluster transforms into Ar(2) (+) solvated by a fluid of neutral argon atoms.

Multireference configuration interaction calculations for the F(P2)+HCl→HF+Cl(P2) reaction: A correlation scaled ground state (1A′2) potential energy surface

This paper presents a new ground state (1 (2)A(')) electronic potential energy surface for the F((2)P)+HCl-->HF+Cl((2)P) reaction. The ab initio calculations are done at the multireference configuration interaction+Davidson correction (MRCI+Q) level of theory by complete basis set extrapolation of the aug-cc-pVnZ (n=2,3,4) energies. Due to low-lying charge transfer states in the transition state region, the molecular orbitals are obtained by six-state dynamically weighted multichannel self-consistent field methods. Additional perturbative refinement of the energies is achieved by implementing simple one-parameter correlation energy scaling to reproduce the experimental exothermicity (DeltaE=-33.06 kcalmol) for the reaction. Ab initio points are fitted to an analytical function based on sum of two- and three-body contributions, yielding a rms deviation of <0.3 kcalmol for all geometries below 10 kcalmol above the barrier. Of particular relevance to nonadiabatic dynamics, the calculations show significant multireference character in the transition state region, which is located 3.8 kcalmol with respect to F+HCl reactants and features a strongly bent F-H-Cl transition state geometry (theta approximately 123.5 degrees ). Finally, the surface also exhibits two conical intersection seams that are energetically accessible at low collision energies. These seams arise naturally from allowed crossings in the C(infinityv) linear configuration that become avoided in C(s) bent configurations of both the reactant and product, and should be a hallmark of all X-H-Y atom transfer reaction dynamics between ((2)P) halogen atoms.

Quantum mechanical investigations of the N(S4)+O2(XΣg−3)→NO(XΠ2)+O(P3) reaction

The reaction between energetic nitrogen atoms and oxygen molecules has received important attention in connection with nitric oxide chemistry in the lower thermosphere. We report time-independent quantum mechanical calculations of the N(S4)+O2→NO+O reaction employing the XA′2 and aA′4 electronic potential energy surfaces of Sayós et al. [J. Chem. Phys. 117, 670 (2002)]. We confirm the production of highly vibrationally excited NO molecules, consistent with previous semiclassical and more recent time-dependent quantum wave packet studies. Calculations are carried out for total angular momentum quantum number J=0 and cross sections and rate coefficients are extracted using the J-shifting approximation. The results are in good agreement with available experimental and theoretical data.

Isotopomer fractionation in the UV photolysis of N2O: Comparison of theory and experiment

In the photodissociation of N2O, absorption cross sections differ with isotopic substitution, leading to a wavelength‐dependent fractionation of the various isotopomers. Several models ranging from shifts by zero‐point energy differences to propagation of wave packets on the excited electronic state potential energy surface have been proposed to explain the observed fractionations. We present time‐independent fractionation calculations for the isotopomers 447, 448, 456, 546, and 556. Besides largely agreeing with the experimental data, these calculations have the advantage of not being computationally intensive, as well as satisfying the physical facts that the asymmetric stretch and the doubly degenerate bending vibration are the principal Franck‐Condon active modes in the photodissociation. The latter is reflected in the actual dissociation and in the high rotational excitation and lack of vibrational excitation of the N2 product. The calculations are based on a multidimensional reflection principle using an ab initio potential energy surface. The theory for the absorption cross section and isotopomer fractionation accompanying photodissociation is described. The absolute value of the theoretically calculated absorption cross section is very close (90%) to the experimentally observed value. The present computations also provide data for the slope of a three‐isotope plot of the fractionation of 447/446 relative to 448/446, using the fractionations at different wavelengths. The resulting slope is compared with a perturbation theoretical expression for direct photodissociation given elsewhere.

A 193nm laser photofragmentation time-of-flight mass spectrometric study of chloroiodomethane

The photodissociation dynamics of chloroiodomethane (CH2ICl) at 193nm has been investigated by employing the photofragment time-of-flight (TOF) mass spectrometric method. Using tunable vacuum ultraviolet undulator synchrotron radiation for photoionization sampling of nascent photofragments, we have identified four primary dissociation product channels: CH2Cl+I(P1∕22)∕I(P3∕22), CH2I+Cl(P1∕22)∕Cl(P3∕22), CHI+HCl, and CH2+ICl. The state-selective detection of I(P3∕22) and I(P1∕22) has allowed the estimation of the branching ratio for I(P1∕22):I(P3∕22) to be 0.73: 0.27. Theoretical calculations based on the time-dependent density-functional theory have been also made to investigate excited electronic potential-energy surfaces, plausible intermediates, and transition structures involved in these photodissociation reactions. The translation energy distributions derived from the TOF measurements suggest that at least two dissociation mechanisms are operative for these photodissociation processes. One involves the direct dissociation from the 2A′1 state initially formed by 193nm excitation, leading to significant kinetic-energy releases. For the I-atom and Cl-atom elimination channels, the fragment kinetic-energy releases observed via this direct dissociation mechanism are consistent with those predicted by the impulsive dissociation models. Other mechanisms are likely predissociative or statistical in nature from the lower 1A′1 and 1A″1 states and/or the ground X̃A′1 state populated by internal conversion from the 2A′1 state. On the basis of the maximum kinetic-energy release for the formation of CH2Cl+I(P1∕22), we have obtained a value of 53±2kcal∕mol for the 0K bond dissociation energy of I–CH2Cl. The intermediates and transition structures for the CHI+HCl and CH2+ICl product channels have been also investigated by ab initio quantum calculations at the MP2(full)∕6-311G(d) and B3LYP(full)∕6-11G(d) levels of theory. The maximum kinetic-energy releases observed for the CHI+HCl and CH2+ICl channels are consistent with the interpretation that the formation of CHI and CH2 in their ground triplet states is not favored.

Impact of Nuclear Quantum Effects on the Molecular Structure of Bihalides and the Hydrogen Fluoride Dimer

The structural impact of nuclear quantum effects is investigated for a set of bihalides, [XHX](-), X = F, Cl, and Br, and the hydrogen fluoride dimer. Structures are calculated with the vibrational self-consistent-field (VSCF) method, the second-order vibrational perturbation theory method (VPT2), and the nuclear-electronic orbital (NEO) approach. In the VSCF and VPT2 methods, the vibrationally averaged geometries are calculated for the Born-Oppenheimer electronic potential energy surface. In the NEO approach, the hydrogen nuclei are treated quantum mechanically on the same level as the electrons, and mixed nuclear-electronic wave functions are calculated variationally with molecular orbital methods. Electron-electron and electron-proton dynamical correlation effects are included in the NEO approach using second-order perturbation theory (NEO-MP2). The nuclear quantum effects are found to alter the distances between the heavy atoms by 0.02-0.05 A for the systems studied. These effects are of similar magnitude as the electron correlation effects. For the bihalides, inclusion of the nuclear quantum effects with the NEO-MP2 or the VSCF method increases the X-X distance. The bihalide X-X distances are similar for both methods and are consistent with two-dimensional grid calculations and experimental values, thereby validating the use of the computationally efficient NEO-MP2 method for these types of systems. For the hydrogen fluoride dimer, inclusion of nuclear quantum effects decreases the F-F distance with the NEO-MP2 method and increases the F-F distance with the VSCF and VPT2 methods. The VPT2 F-F distances for the hydrogen fluoride dimer and the deuterated form are consistent with the experimentally determined values. The NEO-MP2 F-F distance is in excellent agreement with the distance obtained experimentally for a model that removes the large amplitude bending motions. The analysis of these calculations provides insight into the significance of electron-electron and electron-proton correlation, anharmonicity of the vibrational modes, and nonadiabatic effects for hydrogen-bonded systems.

Analysis of the first triad of interacting states (0 2 0), (1 0 0), and (0 0 1) of D 216O from hot emission spectra

The far-infrared and middle-infrared emission spectra of deuterated water vapour were measured at temperatures 1370, 1520, and 1940 K in the ranges 320–860 and 1750–3400 cm −1. The measurements were performed in an alumina cell with an effective length of hot gas of about 50 cm. More than 3550 new measured lines for the D 2 16O molecule corresponding to transitions from highly excited rotational levels of the (0 2 0), (1 0 0), and (0 0 1) vibrational states are reported. These new lines correspond to rotational states with higher values of the rotational quantum numbers compared to previously published determinations: J max = 29 and K a (max) = 22 for the (0 2 0) state, J max = 29 and K a (max) = 25 for the (1 0 0) state, and J max = 30 and K a (max) = 23 for the (0 0 1) state. The extended set of 1987 experimental rotational energy levels for the (0 2 0), (1 0 0), and (0 0 1) vibration states including all previously available data has been determined. For the data reduction we used the generating function model. The root mean square (RMS) deviation between observed and calculated values is 0.004 cm −1 for 1952 rovibrational levels of all three vibration states. A comparison of the observed energy levels with the best available values from the literature and with the global predictions from molecular electronic potential energy surfaces of water isotopic species [H. Partridge, D.W. Schwenke, J. Chem. Phys. 106 (1997) 4618] is discussed. The latter confirms a good consistency of mass-dependent DBOC corrections in the PS potential function with new experimental rovibrational data.

Time-dependent quantum wave-packet description of the π1σ* photochemistry of phenol

The photoinduced hydrogen elimination reaction in phenol via the conical intersections of the dissociative π1σ* state with the π1π* state and the electronic ground state has been investigated by time-dependent quantum wave-packet calculations. A model including three intersecting electronic potential-energy surfaces (S0, π1σ*, and π1π*) and two nuclear degrees of freedom (OH stretching and OH torsion) has been constructed on the basis of accurate ab initio multireference electronic-structure data. The electronic population transfer processes at the conical intersections, the branching ratio between the two dissociation channels, and their dependence on the initial vibrational levels have been investigated by photoexciting phenol from different vibrational levels of its ground electronic state. The nonadiabatic transitions between the excited states and the ground state occur on a time scale of a few tens of femtoseconds if the π1π*-π1σ* conical intersection is directly accessible, which requires the excitation of at least one quantum of the OH stretching mode in the π1π* state. It is shown that the node structure, which is imposed on the nuclear wave packet by the initial preparation as well as by the transition through the first conical intersection (π1π*-π1σ*), has a profound effect on the nonadiabatic dynamics at the second conical intersection (π1σ*-S0). These findings suggest that laser control of the photodissociation of phenol via IR mode-specific excitation of vibrational levels in the electronic ground state should be possible.

A quantum wave-packet study of intersystem crossing effects in the O(P2,1,3,D21)+H2 reaction

We present for the first time an exact quantum study of spin-orbit-induced intersystem crossing effects in the title reaction. The time-dependent wave-packet method, combined with an extended split operator scheme, is used to calculate the fine-structure resolved cross section. The calculation involves four electronic potential-energy surfaces of the 1A' state [J. Dobbyn and P. J. Knowles, Faraday Discuss. 110, 247 (1998)], the 3A' and the two degenerate 3A" states [S. Rogers, D. Wang, A. Kuppermann, and S. Wald, J. Phys. Chem. A 104, 2308 (2000)], and the spin-orbit couplings between them [B. Maiti, and G. C. Schatz, J. Chem. Phys. 119, 12360 (2003)]. Our quantum dynamics calculations clearly demonstrate that the spin-orbit coupling between the triplet states of different symmetries has the greatest contribution to the intersystem crossing, whereas the singlet-triplet coupling is not an important effect. A branch ratio of the spin state Pi32 to Pi12 of the product OH was calculated to be approximately 2.75, with collision energy higher than 0.6 eV, when the wave packet was initially on the triplet surfaces. The quantum calculation agrees quantitatively with the previous quasiclassical trajectory surface hopping study.

Controlled subnanosecond isomerization of HCN to CNH in solution

We report a study of control of the HCN-->CNH isomerization in a liquid Ar solution. We show, using molecular dynamics simulations, nearly complete conversion from HCN to CNH can be achieved in solution on the subnanosecond time scale without requiring laser pulse shaping or molecular alignment. The mechanism of the isomerization reaction involves multiphoton rovibrational excitation on the ground electronic state potential energy surface coupled with rapid rovibrational relaxation in solution. The results demonstrate the important role of rotation-vibration coupling in multiphoton excitation of small molecules and constitute the first realistic computational demonstration of fast, robust, and high-yield laser field manipulation of solution-phase molecular processes.