Theoretical Investigation on Stable Structures and Band Original Shifts of Monomer Vibrations for CF3Cl-CO Complex
NIE Wenbo
WANG Shurui
CHENG Jie
ZHENG Limin
WANG Yan
Abstract：To explore the effect of intermolecular interactions on the intramolecular dynamics of monomers in the complex,the band original shifts of the monomer vibrations for CF3Cl-CO complex were predicted.Firstly,geometry optimizations and vibrational frequency calculations were performed on five structures(S1',S2,S3,S4,and A)of the CF3Cl-CO complex using the second-order Møller-Plesset perturbation method(MP2)in combination with the augmented correlation-consistent triple-zeta basis set(Aug-cc-pVTZ).Secondly,a bond function(3s3p2d1f)was introduced,and the intermolecular interaction energies of these stable configurations were computed using the coupled cluster with single,double,and perturbative triple excitation[CCSD(T)]method with the Aug-cc-pVTZ basis set.The band original shifts of monomer vibrational were then predicted for the most stable structure.The results showed that structure S1' was the most stable configuration with an intermolecular interaction energy of-3.81 kJ/mol.Energy decomposition analysis revealed that the exchange energy contributed the largest portion(38%)to the total interaction energy.Notably,two new stable structures,S4 and A,were found with intermolecular interaction energies of-2.68 kJ/mol and-2.72 kJ/mol,respectively.According to the predicted band origin shifts,the intermolecular halogen bond had a significant impact on the intramolecular dynamics in the S1' structure.Specifically,the C-Cl stretching vibration of the CF3Cl monomer exhibited a red shift in comparison to the free monomer,while the stretching vibration of the CO monomer exhibited a blue shift.The results of this study provided a theoretical foundation for future experimental investigations of the CF3Cl-CO complex.
Keywords：intermolecular interactionsquantum chemical calculationsband original shiftsCF3Cl-CO complexenergy decompositionhalogen bondvan der Waals complex
Publication Date：2025-06-20
Online Publishing Date：2025-08-15(First online date of this platform, not the publication date of the document)
Pages：7( 167-173 )