Skip to main content
OSTI.GOVU.S. Department of Energy Office of Scientific and Technical Information
U.S. Department of Energy
Office of Scientific and Technical Information
 

Spin-Dependent Stereochemistry: A Nonadiabatic Quantum Dynamics Case Study of S + H2 → SH + H Reaction

Journal Article · · Journal of Physical Chemistry Letters
 [1];  [1]
  1. University of Pennsylvania, Philadelphia, PA (United States)
+ Show Author Affiliations
We study the spin-dependent stereodynamics of the S + H2 → SH + H reaction by using full-dimensional quantum dynamics calculations with zero total nuclear angular momentum along the triplet 3A" states and singlet 1A' states. We find that the interplay between the electronic spin direction and the molecular geometry has a measurable influence on the singlet–triplet intersystem crossing reaction probabilities. Our results show that for some incident scattering angles in the body-fixed frame, the relative difference in intersystem crossing reaction probabilities (as determined between spin up and spin down initial states) can be as large as 15%. Furthermore, our findings are an ab initio demonstration of spin-dependent nonadiabatic dynamics, which we hope will shine light as far as understanding the chiral-induced spin selectivity effect.
Research Organization:
University of Pennsylvania, Philadelphia, PA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0019397
OSTI ID:
2510489
Journal Information:
Journal of Physical Chemistry Letters, Journal Name: Journal of Physical Chemistry Letters Journal Issue: 12 Vol. 15; ISSN 1948-7185
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

References (51)

A general method to describe intersystem crossing dynamics in trajectory surface hopping journal March 2015
Chiral Induced Spin Selectivity Gives a New Twist on Spin-Control in Chemistry journal October 2020
Incorporating Berry Force Effects into the Fewest Switches Surface-Hopping Algorithm: Intersystem Crossing and the Case of Electronic Degeneracy journal March 2022
Toward a Unified Analytical Description of Internal Conversion and Intersystem Crossing in the Photodissociation of Thioformaldehyde. I. Diabatic Singlet States journal September 2023
Insight into the Origin of Chiral-Induced Spin Selectivity from a Symmetry Analysis of Electronic Transmission journal April 2020
Increasing the Efficiency of Water Splitting through Spin Polarization Using Cobalt Oxide Thin Film Catalysts journal September 2020
Temperature-Dependent Chiral-Induced Spin Selectivity Effect: Experiments and Theory journal February 2022
Intermediate Coherent–Incoherent Charge Transport: DNA as a Case Study journal October 2016
Modeling Spin-Dependent Nonadiabatic Dynamics with Electronic Degeneracy: A Phase-Space Surface-Hopping Method journal August 2022
Role of the Electron Spin Polarization in Water Splitting journal December 2015
Conservation of Angular Momentum in Direct Nonadiabatic Dynamics journal January 2020
Magnetic field effects in chemical kinetics and related phenomena journal January 1989
A quasiclassical trajectory study of the state-to-state dynamics of atomic hydrogen + water .fwdarw. hydroxyl + molecular hydrogen journal July 1984
Lanczos Subspace Time-Independent Wave Packet Calculations of S (1D) + H2 Reactive Scattering journal June 2002
Importance of Intersystem Crossing in the S( 3 P, 1 D) + H 2 → SH + H Reaction † journal October 2004
How Reactants Polarization Can Be Used to Change and Unravel Chemical Reactivity journal July 2005
Significant Nonadiabatic Effects in the S( 1 D) + HD Reaction journal August 2007
Nonadiabatic Transition State Theory and Trajectory Surface Hopping Dynamics: Intersystem Crossing Between 3 B 1 and 1 A 1 States of SiH 2 journal February 2015
Chiral-Induced Spin Selectivity Effect journal July 2012
Intermediate tunnelling–hopping regime in DNA charge transport journal February 2015
Chiral electrocatalysts eclipse water splitting metrics through spin control journal February 2023
Real-time monitoring of reaction stereochemistry through single-molecule observations of chirality-induced spin selectivity journal May 2023
Chiral molecules and the electron spin journal March 2019
Internal conversion and intersystem crossing dynamics based on coupled potential energy surfaces with full geometry-dependent spin–orbit and derivative couplings. Nonadiabatic photodissociation dynamics of NH3(A) leading to the NH(X3Σ−, a1Δ) + H2 channel journal January 2022
Mixed quantum–classical dynamics journal January 1998
Theoretical studies of intersystem crossing effects in the O+H2 reaction journal December 2000
Theoretical studies of intersystem crossing effects in the O(3P, 1D)+H2 reaction journal December 2003
Bond‐selected bimolecular chemistry: H+HOD(4ν OH )→OD+H 2 journal May 1990
Brute force in molecular reaction dynamics: A novel technique for measuring steric effects journal October 1990
Molecular dynamics with electronic transitions journal July 1990
Quantum reactive scattering with a deep well: Time‐dependent calculation for H+O 2 reaction and bound state characterization for HO 2 journal September 1994
Quasiclassical dynamics for the H + HS abstraction and exchange reactions on the 3A″ and the 3A′ states journal September 2013
Coherent superposition of M-states in a single rovibrational level of H 2 by Stark-induced adiabatic Raman passage journal February 2014
Generalized trajectory surface-hopping method for internal conversion and intersystem crossing journal September 2014
Lorentz-like force emerging from kinematic interactions between electrons and nuclei in molecules: A quantum mechanical origin of symmetry breaking that can trigger molecular chirality journal February 2017
An extension of the fewest switches surface hopping algorithm to complex Hamiltonians and photophysics in magnetic fields: Berry curvature and “magnetic” forces journal March 2019
The Molpro quantum chemistry package journal April 2020
Modeling nonadiabatic dynamics with degenerate electronic states, intersystem crossing, and spin separation: A key goal for chemical physics journal March 2021
Temperature-dependence of the chirality-induced spin selectivity effect—Experiments and theory journal July 2023
Spin-Orbit Coupling Effects in Zinc Blende Structures journal October 1955
Total angular momentum conservation in ab initio Born-Oppenheimer molecular dynamics journal December 2023
Kinetics and Dynamics of the S ( D 2 1 ) + H 2 → SH + H Reaction at Very Low Temperatures and Collision Energies journal November 2010
Pendular states and spectra of oriented linear molecules journal March 1992
Steric Effects in the Chemisorption of Vibrationally Excited Methane on Ni(100) journal July 2010
Spin Selectivity in Electron Transmission Through Self-Assembled Monolayers of Double-Stranded DNA journal February 2011
Partial Control of an Ion-Molecule Reaction by Selection of the Internal Motion of the Polyatomic Reagent Ion journal October 1994
Laser Control of Chemical Reactions journal March 1998
Asymmetric Scattering of Polarized Electrons by Organized Organic Films of Chiral Molecules journal February 1999
Stereodynamical control of the H + HD → H 2 + D reaction through HD reagent alignment journal January 2023
Direct observation of chirality-induced spin selectivity in electron donor–acceptor molecules journal October 2023
Vibrational Control of Bimolecular Reactions with Methane by Mode, Bond, and Stereo Selectivity journal May 2016

Similar Records

Trajectory surface hopping study of the O({sup 3}P) + C{sub 2}H{sub 2} reaction dynamics: Effect of collision energy on the extent of intersystem crossing
Journal Article · Mon Jan 27 23:00:00 EST 2014 · Journal of Chemical Physics · OSTI ID:22255219
Photochemical Au(I)–Au(I) Bond Formation: A Battle between Intersystem Crossing and Internal Conversion
Journal Article · Mon Apr 07 20:00:00 EDT 2025 · Journal of Physical Chemistry Letters · OSTI ID:3011597
Internal conversion and intersystem crossing dynamics based on coupled potential energy surfaces with full geometry-dependent spin–orbit and derivative couplings. Nonadiabatic photodissociation dynamics of NH3(A) leading to the NH(X3Σ–, a1Δ) + H2 channel
Journal Article · Tue Jun 07 00:00:00 EDT 2022 · Physical Chemistry Chemical Physics. PCCP · OSTI ID:1978866

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Chemical calculations
Chemical reactions
Mathematical methods
Quantum mechanics
Scattering