Title: An improved quasi-diabatic representation of the 1, 2, 3¹ A coupled adiabatic potential energy surfaces of phenol in the full 33 internal coordinates

Abstract

In a previous project we constructed a quasi-diabatic representation, H^d, of the 1, 2, 3¹A adiabatic states of phenol from high level multireference single and double excitation configuration interaction electronic structure data, energies, energy gradients, and derivative couplings. That H^d accurately describes surface minima, saddle points, and also regions of strong nonadiabatic interactions, reproducing the locus of conical intersection seams and the coordinate dependence of the derivative couplings. The present work determines the accuracy of H^d for describing phenol photodissociation. Additionally, we demonstrate that a modest energetic shift of two diabats yields a quantifiably more accurate H^d compared with experimental energetics. The analysis shows that in favorable circumstances it is possible to use single point energies obtained from the most reliable electronic structure methods available, including methods for which the energy gradients and derivative couplings are not available, to improve the quality of a global representation of several coupled potential energy surfaces. Our data indicate an alternative interpretation of kinetic energy release measurements near λ_phot ~ 248 nm.

Authors:

Zhu, Xiaolei  ^[1];

• Search DOE PAGES for author "Zhu, Xiaolei"
• Search DOE PAGES for ORCID "0000-0002-7825-4815"

Malbon, Christopher L. ^[1]; Yarkony, David R.  ^[1]

• Search DOE PAGES for author "Yarkony, David R."
• Search DOE PAGES for ORCID "0000-0002-5446-1350"

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+ Show Author Affiliations

1. Johns Hopkins Univ., Baltimore, MD (United States)

Publication Date:

Thu Mar 31 00:00:00 EDT 2016

Research Org.:

Johns Hopkins Univ., Baltimore, MD (United States); University of California, Berkeley, CA (United States)

Sponsoring Org.:

USDOE Office of Science (SC), Basic Energy Sciences (BES)

OSTI Identifier:

1599341

Alternate Identifier(s):

OSTI ID: 1421161

Grant/Contract Number:  

FG02-91ER14189; AC02-5CH11231

Resource Type:

Accepted Manuscript

Journal Name:

Journal of Chemical Physics

Additional Journal Information:

Journal Volume: 144; Journal Issue: 12; Journal ID: ISSN 0021-9606

Publisher:

American Institute of Physics (AIP)

Country of Publication:

United States

Language:

English

Subject:

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY