Theoretical study on the photoelectron spectra of ozone

• Main Authors: Lin, Ting-iun, 林亭妘
• Other Authors: Chang, Jia-lin
• Format: Others
• Language: zh-TW
• Published: 2009
• Online Access: http://ndltd.ncl.edu.tw/handle/42507984466131628969

碩士 === 國立臺中教育大學 === 科學應用與推廣學系科學教育碩士班 === 98 === In this study, the equilibrium geometries and harmonic vibrational frequencies of the ground states of ozone (O3), cation (O3+), and ozonide (O3-) were calculated by using the B3LYP method of the density functional theory, together with 6-311+G(d), 6-311+G(2d), 6-311+G(3d), 6-311+G(3df) basis sets. More accurate results were obtained by the CCSD(T) method of the coupled cluster theory with two extra basis sets, cc-pVTZ and aug-cc-pVTZ (AVTZ). The adiabatic ionization energy (AIE) and electron affinity (EA) of ozone were computed by using the CCSD(T) method and extrapolated to the complete basis set (CBS) limit with aug-cc-pVXZ (X = D, T, Q, 5). It was found that the simulated spectra were in agreement with the experiment. The photoelectron spectra of O3 were mainly composed of ν2 progressions and the combination bands of ν1 and ν2; the simulated photoelectron spectra of O3- were mainly composed of ν1 progressions and the combination bands of ν1 and ν2. The adiabatic ionization energy of O3 is calculated to be 12.50 and 12.58 eV for AVTZ and CBS, respectively, which is in agreement with the experiment within 0.02 and 0.06 eV, respectively. The electron affinity of O3 is calculated to be 2.109 eV and 2.141 eV for AVTZ and CBS, respectively, which is in agreement with the experiment within 0.006 and 0.038 eV, respectively. In both ionization energy and electron affinity calculations, the errors of AVTZ are smaller than those of CBS.