Molecular symmetry properties of conical intersections and nonadiabatic coupling terms: theory and quantum chemical demonstration for cyclopenta-2,4-dienimine (C5H4NH).

@article{AlJabour2010MolecularSP,
  title={Molecular symmetry properties of conical intersections and nonadiabatic coupling terms: theory and quantum chemical demonstration for cyclopenta-2,4-dienimine (C5H4NH).},
  author={Salih Al-Jabour and Michael Baer and Omar El Deeb and M Leibscher and J{\"o}rn Manz and X F Xu and Shmuel Zilberg},
  journal={The journal of physical chemistry. A},
  year={2010},
  volume={114 9},
  pages={
          2991-3010
        }
}
This paper discovers molecular symmetry (MS) properties of conical intersections (CIs) and the related nonadiabatic coupling terms (NACTs) in molecules which allow large amplitude motions such as torsion, in the frame of the relevant molecular symmetry group, focusing on groups with one-dimensional (1-d) irreducible representations (IREPs). If one employs corresponding MS-adapted nuclear coordinates, the NACTs can be classified according to those IREPs. The assignment is supported by theorems… 
32 Citations

Figures and Tables from this paper

Construction of diabatic Hamiltonian matrix from ab initio calculated molecular symmetry adapted nonadiabatic coupling terms and nuclear dynamics for the excited states of Na3 cluster.
We present the molecular symmetry (MS) adapted treatment of nonadiabatic coupling terms (NACTs) for the excited electronic states (2(2)E' and 1(2)A1') of Na3 cluster, where the adiabatic potential
Ab initio constructed diabatic surfaces of NO2 and the photodetachment spectra of its anion.
TLDR
The analytic expressions for the adiabatic PESs and ADT angles are provided to represent a two-state three-mode diabatic Hamiltonian of NO2 for performing nuclear dynamics to calculate the photo-electron spectra of its anion.
Conical intersections and diabatic potential energy surfaces for the three lowest electronic singlet states of H3 (+).
TLDR
The beyond Born-Oppenheimer approach could incorporate the effect of NACTs accurately and construct single-valued, continuous, smooth, and symmetric diabatic PESs.
Effects of molecular symmetry on quantum reaction dynamics: novel aspects of photoinduced nonadiabatic dynamics.
TLDR
It is shown that the nuclear spin of the system determines the symmetry of the initial nuclear wave function and thus influences the torsional dynamics, which may open new possibilities for nuclear spin selective laser control of nuclear dynamics.
Renner-Teller intersections along the collinear axes of polyatomic molecules: H2CN as a case study.
TLDR
The present article is devoted to another tetra-atomic molecule, namely, the H(2)CN molecule, which just like the C( 2)H(2)(+) ion, is characterized by Renner-Teller intersections along its collinear axis, and the extension of (the two-state) Berry (topological) phase to situations with numerous strongly interacting states.
Study of Topological Effects Concerning the Lowest A″ and the Three A' States for the CO2(+) Ion.
TLDR
A study of the topological effects in CO2(+) has been carried out by calculating nonadiabatic coupling terms (NACTs) at the state-averaged CASSCF level using the cc-pVTZ basis set for the lowest three A' states and one A″ state along a circular contour.
The role of electron-nuclear coupling on multi-state photoelectron spectra, scattering processes and phase transitions.
We present first principle based beyond Born-Oppenheimer (BBO) theory and its applications on various models as well as realistic spectroscopic and scattering processes, where the Jahn-Teller (JT)
A tri-atomic Renner-Teller system entangled with Jahn-Teller conical intersections.
TLDR
The present study is characterized by planar contours that intersect the collinear axis, thus, forming a unique type of RT-non-adiabatic coupling terms (NACT) expressed in terms of Dirac-δ functions, and reveals an unexpected result of the following kind.
The adiabatic-to-diabatic transformation angle and the berry phase for coupled jahn–teller/renner–teller systems: The F + H2 as a case study
The approach to calculate improved, two-state, adiabatic-to-diabatic transformation angles (also known as mixing angles), presented before (see Das et al., J Chem Phys 2010, 133, 084107), was used
Dressed adiabatic and diabatic potentials to study conical intersections for F + H2.
TLDR
According to this study, the most one should expect, in case of F + H(2), is a mild effect of the (1, 2) ci on its reactive/exchange process--an outcome also supported by experiment.
...
1
2
3
4
...

References

SHOWING 1-5 OF 5 REFERENCES
The role of degenerate states in chemistry
Early Perspectives on Geometric Phase (M. S. Child).The Electronic Non-Adiabatic Coupling Term in Molecular Systems: A Theoretical Approach (By Michael Baer).Non-Adiabatic Effects in Chemical
Beyond Born-Oppenheimer : conical intersections and electronic nonadiabatic coupling terms
Preface. Abbreviations. 1. Mathematical Introduction. I.A. The Hilbert Space. I.A.1. The Eigenfunction and the Electronic non-Adiabatic Coupling Term. I.A.2. The Abelian and the non-Abelian Curl
Molecular symmetry and spectroscopy
  • P. Bunker, F. A. Matsen
  • Environmental Science
  • 1979
Editorial Board: W. G. E. Caldwell, OC, FRSC (University of Western Ontario); K. G. Davey, OC, FRSC (York University); S. Gubins (Annual Reviews); B. K. Hall, FRSC (Dalhousie University); P.
Dynamics of molecules and chemical reactions
Spectra, rates, and intranolecular dynamics quantum mechanical studies of molecular spectra and dynamics picturing quantized intranolecular vibrational energy flow: action diffusion, localization,