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Title: Analytical derivatives of the individual state energies in ensemble density functional theory method. I. General formalism

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.4994542· OSTI ID:1390315
 [1]; ORCiD logo [2]; ORCiD logo [2]
  1. Ulsan National Inst. of Science and Technology (UNIST), Ulsan (South Korea). Dept. of Chemistry
  2. Stanford Univ., CA (United States). Dept. of Chemistry, PULSE Inst.
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The state-averaged (SA) spin restricted ensemble referenced Kohn-Sham (REKS) method and its state interaction (SI) extension, SI-SA-REKS, enable one to describe correctly the shape of the ground and excited potential energy surfaces of molecules undergoing bond breaking/bond formation reactions including features such as conical intersections crucial for theoretical modeling of non-adiabatic reactions. Until recently, application of the SA-REKS and SI-SA-REKS methods to modeling the dynamics of such reactions was obstructed due to the lack of the analytical energy derivatives. Here, the analytical derivatives of the individual SA-REKS and SI-SA-REKS energies are derived. The final analytic gradient expressions are formulated entirely in terms of traces of matrix products and are presented in the form convenient for implementation in the traditional quantum chemical codes employing basis set expansions of the molecular orbitals. Finally, we will describe the implementation and benchmarking of the derived formalism in a subsequent article of this series.

Research Organization:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC02-76SF00515
OSTI ID:
1390315
Journal Information:
Journal of Chemical Physics, Vol. 147, Issue 3; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 46 works
Citation information provided by
Web of Science

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Exploiting graphical processing units to enable quantum chemistry calculation of large solvated molecules with conductor-like polarizable continuum models journal October 2018
A 3‐D bonding perspective of the factors influencing the relative stability of the S 1 /S 0 conical intersections of the penta‐2,4‐dieniminium cation (PSB3) journal January 2019
Next‐generation quantum theory of atoms in molecules for the photochemical ring‐opening reactions of oxirane journal April 2019
Next‐generation quantum theory of atoms in molecules for the S 1 /S 0 conical intersections in dynamics trajectories of a light‐driven rotary molecular motor journal November 2019
Theoretical modelling of the dynamics of primary photoprocess of cyclopropanone journal January 2019
Design and photoisomerization dynamics of a new family of synthetic 2-stroke light driven molecular rotary motors journal January 2019
Non-adiabatic dynamics of ring opening in cyclohexa-1,3-diene described by an ensemble density-functional theory method journal June 2018
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Non-adiabatic dynamics of ring opening in cyclohexa-1,3-diene described by an ensemble density-functional theory method text January 2018

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
71 CLASSICAL AND QUANTUM MECHANICS
GENERAL PHYSICS