Continuous surface switching: An improved time-dependent self-consistent-field method for nonadiabatic dynamics

We present a new semiclassical method for electronically nonadiabatic collisions. The method is a variant of the time-dependent self-consistent-field method and is called continuous surface switching. The algorithm involves a self-consistent potential trajectory surface switching approach that is designed to combine the advantages of the trajectory surface hopping approach and the Ehrenfest classical path self-consistent potential approach without their relative disadvantages. Viewed from the self-consistent perspective, it corresponds to “on-the-fly histogramming” of the Ehrenfest method by a natural decay of mixing; viewed from the surface hopping perspective, it corresponds to replacing discontinuous surface hops by continuous surface switching. In this article we present the method and illustrate it for three multidimensional cases. Accurate quantum mechanical scattering calculations are carried out for these three cases by a linear algebraic variational method, and the accurate values of reactive pro...

[1]  Donald G. Truhlar,et al.  QUANTUM MECHANICAL AND QUASICLASSICAL TRAJECTORY SURFACE HOPPING STUDIES OF THE ELECTRONICALLY NONADIABATIC PREDISSOCIATION OF THE A STATE OF NAH2 , 1999 .

[2]  P. J. Kuntz,et al.  Classical path surface‐hopping dynamics. I. General theory and illustrative trajectories , 1991 .

[3]  Donald G. Truhlar,et al.  Trajectory‐surface‐hopping study of Na(3p 2P) +H2 → Na(3s 2S)+H2(v′, j′, θ) , 1983 .

[4]  E. Burhop.  Theory of Collisions , 1961 .

[5]  M. Tachiya,et al.  Non-adiabatic effects in condensed phase activated rate processes in the near-adiabatic limit , 1998 .

[6]  Yi Ping Liu,et al.  Validation of trajectory surface hopping methods against accurate quantum mechanical dynamics and semiclassical analysis of electronic-to-vibrational energy transfer , 1997 .

[7]  W. Miller,et al.  Semiclassical molecular dynamics simulations of ultrafast photodissociation dynamics associated with the Chappuis band of ozone , 1998 .

[8]  S. Sato,et al.  Potential Energy Surface of the System of Three Atoms , 1955 .

[9]  K. J. McCann,et al.  Vibrational deactivation of oxygen ions in low velocity 02+(X2Πg,υ=1)+02(X 3Σg−,υ=0) collisions , 1981 .

[10]  Donald G. Truhlar,et al.  Are Semiclassical Methods Accurate for Electronically Nonadiabatic Transitions between Weakly Coupled Potential Energy Surfaces , 1999 .

[11]  Craig C. Martens,et al.  Semiclassical-limit molecular dynamics on multiple electronic surfaces , 1997 .

[12]  J. Durup.  Angular momentum conservation in hemiquantal dynamics , 1990 .

[13]  Michael F. Herman.  Optimal representation for semiclassical surface hopping methods , 1999 .

[14]  William H. Miller.  Dynamics of Molecular Collisions , 1976 .

[15]  P. Rossky,et al.  Nonadiabatic molecular dynamics simulation of photoexcitation experiments for the solvated electron in methanol , 1999 .

[16]  J. Joens,et al.  Temperature dependent near-UV molar absorptivities of aliphatic aldehydes and ketones in aqueous solution , 1993 .

[17]  D. Truhlar,et al.  Test of Trajectory Surface Hopping Against Accurate Quantum Dynamics for an Electronically Nonadiabatic Chemical Reaction , 1998 .

[18]  W. Miller,et al.  A classical analog for electronic degrees of freedom in nonadiabatic collision processes , 1979 .

[19]  Thom Vreven,et al.  Potential-energy surfaces for ultrafast photochemistry Static and dynamic aspects , 1998 .

[20]  A. Depristo.  A test of the semiclassical energy conserving trajectory technique for low energy electron transfer reactions , 1983 .

[21]  D. G. Imre,et al.  Mixed quantum wave packet/classical trajectory treatment of the photodissociation process ArHCl→Ar+H+Cl , 1992 .

[22]  D. Sholl,et al.  A generalized surface hopping method , 1998 .

[23]  Donald L Thompson,et al.  Modern Methods for Multidimensional Dynamics Computations in Chemistry , 1998 .

[24]  O. Prezhdo.  Mean field approximation for the stochastic Schrödinger equation , 1999 .

[25]  S. Hammes-Schiffer,et al.  Excited state dynamics with nonadiabatic transitions for model photoinduced proton-coupled electron transfer reactions , 1997 .

[26]  S. Iwata,et al.  Photodissociation dynamics of Ar+3 , 1993 .

[27]  D. Truhlar,et al.  Variational reactive scattering calculations: computational optimization strategies , 1991 .

[28]  J. Durup.  Again on the half-trajectory matching method in quasi-classical calculations of reaction dynamics , 1988 .

[29]  R. Kosloff,et al.  Quantum mechanism in the photodissociation of NaFH complex: a challenge to semiclassical analysis , 1999 .

[30]  Schwenke,et al.  Dynamical basis sets for algebraic variational calculations in quantum-mechanical scattering theory. , 1990, Physical review. A, Atomic, molecular, and optical physics.

[31]  A. Ferretti,et al.  Quantum dynamics of a model system with a conical intersection , 1997 .

[32]  R. J. Cross.  Semiclassical Theory of Inelastic Scattering: An Infinite‐Order Distorted‐Wave Approximation , 1968 .

[33]  Amrendra Vijay,et al.  Semiclassical wave packet calculations on ion–molecule reactions: Studies on B+(3Pu)+H2 reaction , 1997 .

[34]  Richard B. Bernstein,et al.  Atom - Molecule Collision Theory , 1979 .

[35]  Todd J. Martínez,et al.  Ab initio/interpolated quantum dynamics on coupled electronic states with full configuration interaction wave functions , 1999 .

[36]  D. Truhlar,et al.  A new diabatic representation of the coupled potential energy surfaces for Na(3p 2P)+H2→Na(3s 2S)+H2 or NaH+H , 1992 .

[37]  B. Berne,et al.  Nonradiative relaxation processes in condensed phases: Quantum versus classical baths , 1999 .

[38]  David A. Micha,et al.  A self‐consistent eikonal treatment of electronic transitions in molecular collisions , 1983 .

[39]  Yuri L. Volobuev,et al.  Do Semiclassical Trajectory Theories Provide an Accurate Picture of Radiationless Decay for Systems with Accessible Surface Crossings , 2000 .

[40]  H. L. Rouzo,et al.  Hemiquantal time dependent calculation of the absorption spectrum of a photodissociating triatomic , 1992 .

[41]  A. Douglas,et al.  The Electronic Spectrum of HF. I. The B1Σ+–X1Σ+ Band System , 1973 .

[42]  Masakatsu Ito,et al.  Nonadiabatic transition and energy relaxation dynamics in the photoisomerization of s-trans butadiene , 1997 .

[43]  D. Truhlar,et al.  Algebraic variational and propagation formalisms for quantal dynamics calculations of electronic‐to‐vibrational, rotational energy transfer and application to the quenching of the 3p state of sodium by hydrogen molecules , 1994 .

[44]  R. Krems,et al.  Semiclassical Wave Packet Dynamics with Electronic Structure Computed on the Fly: Application to Photophysics of Electronic Excited States in Condensed Phase , 1999 .

[45]  Rudolph E. Langer,et al.  On the Connection Formulas and the Solutions of the Wave Equation , 1937 .

[46]  D. Truhlar,et al.  Statistical model for nonadiabatic decay of an exciplex strongly coupled to a dissociative continuum , 1997 .

[47]  D. Coker,et al.  Nonadiabatic molecular dynamics simulations of the photofragmentation and geminate recombination dynamics in size-selected I2−⋅Arn cluster ions , 1997 .

[48]  Lichang Wang.  A quenching method in mixed quantum-classical dynamics calculations on nonadiabatic problems , 1998 .

[49]  N. S. Bayliss,et al.  Solvent effects on the intensities of the weak ultraviolet spectra of ketones and nitroparaffins—I , 1968 .

[50]  Hiroki Nakamura,et al.  Semiclassical theory of multi-channel curve crossing problems: Landau-Zener case , 1997 .

[51]  M. Persico,et al.  Semiclassical treatment of the photofragmentation of azomethane , 1998 .

[52]  Garth A. Jones,et al.  Application of Trajectory Surface Hopping to the Study of a Symmetry-Forbidden Intramolecular Hole Transfer Process in Bismethyleneadamantane Cation Radical , 1999 .

[53]  W. Miller,et al.  Classical trajectory model for electronically nonadiabatic collision phenomena. A classical analog for electronic degrees of freedom , 1978 .

[54]  G. Stock,et al.  Flow of zero-point energy and exploration of phase space in classical simulations of quantum relaxation dynamics. II. Application to nonadiabatic processes , 1999 .

[55]  Alexander Dalgarno,et al.  Thermal scattering of atoms by homonuclear diatomic molecules , 1963, Proceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences.

[56]  D. Herschbach,et al.  EMPIRICAL EVALUATION OF THE LONDON POTENTIAL ENERGY SURFACE FOR THE H + H2. REACTION , 1964 .

[57]  J. Tully.  Molecular dynamics with electronic transitions , 1990 .

[58]  C. Mead,et al.  Conditions for the definition of a strictly diabatic electronic basis for molecular systems , 1982 .

[59]  H. Rabitz,et al.  The classical path approximation in time‐dependent quantum collision theory , 1978 .