The anion photoelectron spectrum and diabatization of tetrazolyl

The potential energy surface of tetrazolyl [cyclic (N4CH)] has a conical intersection seam between the two lowest-energy electronic states near the ground state minimum geometry. This work treats that molecule. The potential energy surfaces used in this study are based on a least-squares fitting pro...

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Bibliographic Details
Published in:The Journal of chemical physics 2024-06, Vol.160 (21)
Main Authors: Avanessian, Chris, Yarkony, David R.
Format: Article
Language:English
Subjects:
Anions
Configuration interaction
Couplings
Electron states
Energy gradient
Photoelectrons
Polynomials
Potential energy
Ultraviolet spectra
Wave functions
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Summary:The potential energy surface of tetrazolyl [cyclic (N4CH)] has a conical intersection seam between the two lowest-energy electronic states near the ground state minimum geometry. This work treats that molecule. The potential energy surfaces used in this study are based on a least-squares fitting procedure that includes ab initio energies, energy gradients, and derivative couplings described using polynomials up to fourth-order and ab initio data obtained from multireference configuration interaction wave functions. A five-electronic-state description was generated with a root mean square absolute energy error of 9.6 cm–1, compared to 326.8 cm–1 when only second-order terms were used. The time-independent multimode vibronic coupling in the KDC approximation was used to simulate and analyze the anion ultraviolet photoelectron spectrum of tetrazolide.
ISSN:0021-9606
1089-7690
DOI:10.1063/5.0214635