Journal ArticleDOI
Nonadiabatic coupling of the 1 1A″ and 2 1A″ states of ozone
Thomas Neuheuser,Nagamani Sukumar,Sigrid D. Peyerimhoff +2 more
- Vol. 194, Iss: 1, pp 45-64
Reads0
Chats0
TLDR
In this article, the first-derivative nonadiabatic Born coupling terms for the two lowest-lying singlet A-excited states of ozone (1 A 2 and 1 B 1 in C 2v symmetry) whose electronic potential energy surfaces exhibit a crossing at a bond angle near 120° were derived.Abstract:
We report the results of ab initio calculations of the nonadiabatic Born coupling terms for the two lowest-lying singlet A″ excited states of ozone ( 1 A 2 and 1 B 1 in C 2v symmetry) whose electronic potential energy surfaces exhibit a crossing at a bond angle near 120°. Since photoexcitation from the ground state to these A″ states is believed to be responsible for the Chappuis band of ozone, determination of the nonadiabatic coupling terms in the molecular Hamiltonian is therefore likely to be of importance in understanding the predissociative features of the spectrum. The nuclear derivative coupling matrix elements are computed between ab initio electronic wavefunctions obtained from multi-reference configuration interaction (MRD-CI) calculations in a basis of configuration state functions constructed from MCSCF orbitals. The first-derivative nonadiabatic coupling terms are calculated analytically in a manner similar to the calculation of analytic energy gradients, thereby avoiding the cumbersome numerical differentiation of CI and SCF coefficients. The calculated analytical derivative coupling matrix elements are used to determine a suitable transformation to a quasidiabatic basis.read more
Citations
More filters
Journal ArticleDOI
First-order nonadiabatic couplings from time-dependent hybrid density functional response theory: Consistent formalism, implementation, and performance
Robert Send,Filipp Furche +1 more
TL;DR: A time-dependent response approach to NACMEs which avoids explicit computation of excited-state wave functions is outlined and the Chernyak-Mukamel formula is shown to be equivalent to the Hellmann-Feynman contribution in analytical gradient theory.
Book ChapterDOI
Theory of Ultrafast Nonadiabatic Excited‐State Processes and their Spectroscopic Detection in Real Time
Wolfgang Domcke,Gerhard Stock +1 more
Journal ArticleDOI
The direct calculation of diabatic states based on configurational uniformity
Hisao Nakamura,Donald G. Truhlar +1 more
TL;DR: In this article, the diabatization procedure of Atchity and Ruedenberg is extended to include more general types of crossings and avoided crossings of potential energy surfaces, which is more general than the previously proposed occupation number and natural orbital method, and remains valid even for chemical reactions that require multiple diabatic prototypes.
Journal ArticleDOI
The effects of couplings to symmetric and antisymmetric modes and minor asymmetry on the spectral properties of mixed-valence and related charge-transfer systems
Jeffrey R. Reimers,Noel S. Hush +1 more
TL;DR: In this paper, the authors explore the relationship between symmetric and antisymmetric modes, concentrating on how this is modified by the presence of weak (e.g., environmentally or substitutionally induced) asymmetry.
Journal ArticleDOI
Discrete variable approaches to tetratomic molecules: part I: DVR(6) and DVR(3) + DGB methods.
TL;DR: Vibrationally averaged geometries, expectation values of rotational constants, and several adiabatic projection schemes developed in this work for tetratomic molecules are used to characterize the vibrational levels calculated by the DVR(6) and DVR (3) + DGB.
References
More filters
Journal ArticleDOI
Energy Extrapolation in CI Calculations
TL;DR: In this paper, a method of extrapolating the CI energy of large configuration subspaces is discussed and illustrated in a series of examples, while the influence of the remaining elements in the subspace is accounted for in a statistical manner.
Journal ArticleDOI
General Setting for Berry's Phase
Joseph Samuel,Rajendra Bhandari +1 more
TL;DR: It is shown that Berry's phase appears in a more general context than realized so far, using some ideas introduced by Pancharatnam in his study of the interference of polarized light to allow a meaningful comparison of the phase between any two nonorthogonal vectors in Hilbert space.
Journal ArticleDOI
On the evaluation of analytic energy derivatives for correlated wave functions
TL;DR: In this article, it was shown that to obtain the (2n)th and ( 2n+1)th energy gradients, it is only necessary to solve equations of the difficulty of the nth order coupled perturbed equations for the orbital and configuration interaction (CI) parameters.
Journal ArticleDOI
On the determination of Born–Oppenheimer nuclear motion wave functions including complications due to conical intersections and identical nuclei
C. Alden Mead,Donald G. Truhlar +1 more
TL;DR: In this article, the authors show how permutational symmetry of the total wave function with respect to interchange of nuclei can be enforced in the Born-Oppenheimer approximation both in the absence and the presence of conical intersections.
Journal ArticleDOI
Conditions for the definition of a strictly diabatic electronic basis for molecular systems
C. Alden Mead,Donald G. Truhlar +1 more
TL;DR: In this paper, a strictly diabatic electronic basis is defined as one for which all components of the nuclear momentum coupling vanish, and it is shown that such a basis does not exist.
Related Papers (5)
Direct construction of diabatic states in the CASSCF approach. Application to the conical intersection of the 1A2 and 1B1 excited states of ozone
Wolfgang Domcke,Clemens Woywod +1 more