skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Theoretical studies for the N{sub 2}–N{sub 2}O van der Waals complex: The potential energy surface, intermolecular vibrations, and rotational transition frequencies

Abstract

Theoretical studies of the potential energy surface (PES) and bound states are performed for the N{sub 2}–N{sub 2}O van der Waals (vdW) complex. A four-dimensional intermolecular PES is constructed at the level of single and double excitation coupled-cluster method with a non-iterative perturbation treatment of triple excitations [CCSD(T)] with aug-cc-pVTZ basis set supplemented with bond functions. Two equivalent T-shaped global minima are located, in which the O atom of N{sub 2}O monomer is near the N{sub 2} monomer. The intermolecular fundamental vibrational states are assigned by inspecting the orientation of the nodal surface of the wavefunctions. The calculated frequency for intermolecular disrotation mode is 23.086 cm{sup −1}, which is in good agreement with the available experimental data of 22.334 cm{sup −1}. A negligible tunneling splitting with the value of 4.2 MHz is determined for the ground vibrational state and the tunneling splitting increases as the increment of the vibrational frequencies. Rotational levels and transition frequencies are calculated for both isotopomers {sup 14}N{sub 2}–N{sub 2}O and {sup 15}N{sub 2}–N{sub 2}O. The accuracy of the PES is validated by the good agreement between theoretical and experimental results for the transition frequencies and spectroscopic parameters.

Authors:
 [1];  [2]; ;  [1];  [3]
  1. Key Laboratory of Magnetic Resonance in Biological Systems, State Key Laboratory of Magnetic Resonance and Atomic and Molecular Physics, Wuhan Centre for Magnetic Resonance, Wuhan Institute of Physics and Mathematics, Chinese Academy of Sciences, Wuhan 430071 (China)
  2. (China)
  3. Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, 21 Nanyang Link, Singapore 637371 (Singapore)
Publication Date:
OSTI Identifier:
22493129
Resource Type:
Journal Article
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 143; Journal Issue: 15; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0021-9606
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ACCURACY; BOUND STATE; DISTURBANCES; EXCITATION; FOUR-DIMENSIONAL CALCULATIONS; MHZ RANGE; NITROUS OXIDE; PERTURBATION THEORY; POTENTIAL ENERGY; SURFACES; TUNNEL EFFECT; VAN DER WAALS FORCES; VIBRATIONAL STATES; WAVE FUNCTIONS

Citation Formats

Zheng, Rui, School of Mathematics and Information Science, North China University of Water Resources and Electric Power, Zhengzhou 450011, Zheng, Limin, Yang, Minghui, E-mail: yplu@ntu.edu.sg, E-mail: yangmh@wipm.ac.cn, and Lu, Yunpeng, E-mail: yplu@ntu.edu.sg, E-mail: yangmh@wipm.ac.cn. Theoretical studies for the N{sub 2}–N{sub 2}O van der Waals complex: The potential energy surface, intermolecular vibrations, and rotational transition frequencies. United States: N. p., 2015. Web. doi:10.1063/1.4933057.
Zheng, Rui, School of Mathematics and Information Science, North China University of Water Resources and Electric Power, Zhengzhou 450011, Zheng, Limin, Yang, Minghui, E-mail: yplu@ntu.edu.sg, E-mail: yangmh@wipm.ac.cn, & Lu, Yunpeng, E-mail: yplu@ntu.edu.sg, E-mail: yangmh@wipm.ac.cn. Theoretical studies for the N{sub 2}–N{sub 2}O van der Waals complex: The potential energy surface, intermolecular vibrations, and rotational transition frequencies. United States. doi:10.1063/1.4933057.
Zheng, Rui, School of Mathematics and Information Science, North China University of Water Resources and Electric Power, Zhengzhou 450011, Zheng, Limin, Yang, Minghui, E-mail: yplu@ntu.edu.sg, E-mail: yangmh@wipm.ac.cn, and Lu, Yunpeng, E-mail: yplu@ntu.edu.sg, E-mail: yangmh@wipm.ac.cn. Wed . "Theoretical studies for the N{sub 2}–N{sub 2}O van der Waals complex: The potential energy surface, intermolecular vibrations, and rotational transition frequencies". United States. doi:10.1063/1.4933057.
@article{osti_22493129,
title = {Theoretical studies for the N{sub 2}–N{sub 2}O van der Waals complex: The potential energy surface, intermolecular vibrations, and rotational transition frequencies},
author = {Zheng, Rui and School of Mathematics and Information Science, North China University of Water Resources and Electric Power, Zhengzhou 450011 and Zheng, Limin and Yang, Minghui, E-mail: yplu@ntu.edu.sg, E-mail: yangmh@wipm.ac.cn and Lu, Yunpeng, E-mail: yplu@ntu.edu.sg, E-mail: yangmh@wipm.ac.cn},
abstractNote = {Theoretical studies of the potential energy surface (PES) and bound states are performed for the N{sub 2}–N{sub 2}O van der Waals (vdW) complex. A four-dimensional intermolecular PES is constructed at the level of single and double excitation coupled-cluster method with a non-iterative perturbation treatment of triple excitations [CCSD(T)] with aug-cc-pVTZ basis set supplemented with bond functions. Two equivalent T-shaped global minima are located, in which the O atom of N{sub 2}O monomer is near the N{sub 2} monomer. The intermolecular fundamental vibrational states are assigned by inspecting the orientation of the nodal surface of the wavefunctions. The calculated frequency for intermolecular disrotation mode is 23.086 cm{sup −1}, which is in good agreement with the available experimental data of 22.334 cm{sup −1}. A negligible tunneling splitting with the value of 4.2 MHz is determined for the ground vibrational state and the tunneling splitting increases as the increment of the vibrational frequencies. Rotational levels and transition frequencies are calculated for both isotopomers {sup 14}N{sub 2}–N{sub 2}O and {sup 15}N{sub 2}–N{sub 2}O. The accuracy of the PES is validated by the good agreement between theoretical and experimental results for the transition frequencies and spectroscopic parameters.},
doi = {10.1063/1.4933057},
journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 15,
volume = 143,
place = {United States},
year = {2015},
month = {10}
}