TY - JOUR
T1 - Vibronic coupling and Jahn-Teller effects in negatively charged [30]annulene
AU - Kato, Takashi
AU - Yoshizawa, Kazunari
AU - Yamabe, Tokio
N1 - Funding Information:
This work was supported by the “Research for the Future” Program from the Japan Society for the Promotion of Science (JSPS-RFTF96P00206) and by a Grant-in-Aid for Scientific Research on the Priority Area “Carbon Alloys” from the Ministry of Education, Science, Sports and Culture of Japan. T.K. is grateful to the JSPS for a graduate fellowship. Computational time was provided by the Supercomputer Laboratory, Institute for Chemical Research of Kyoto University as well as by the Computer Center of the Institute for Molecular Science.
PY - 1999/9/1
Y1 - 1999/9/1
N2 - The vibronic interactions and Jahn-Teller distortions in the mono- and trianions of [30]annulene are discussed comparatively with those of benzene and [18]annulene. We calculate the electronic structures, vibrational modes, and linear vibronic coupling constants of [30]annulene as well as its deutero-form using the B3LYP method, the hybrid density functional theory method of Becke and Lee, Yang, and Parr. The lowest-frequency E2g mode of 38 cm-1 which causes deformation of the carbon ring is important compared to any other mode in causing the Jahn-Teller distortions. Such a low-frequency vibrational mode is characteristic of nanosized molecular systems, being analogous to acoustic mode of phonon in solid. We find that such a vibrational mode plays an important role in the Jahn-Teller distortions as the ring size of annulene becomes large from benzene to [30]annulene. We also study the H/D isotope effect and find that the vibronic coupling constant of the E2g mode of 1513 cm-1 becomes larger by substituting deuteriums for hydrogens in negatively charged [30]annulene.
AB - The vibronic interactions and Jahn-Teller distortions in the mono- and trianions of [30]annulene are discussed comparatively with those of benzene and [18]annulene. We calculate the electronic structures, vibrational modes, and linear vibronic coupling constants of [30]annulene as well as its deutero-form using the B3LYP method, the hybrid density functional theory method of Becke and Lee, Yang, and Parr. The lowest-frequency E2g mode of 38 cm-1 which causes deformation of the carbon ring is important compared to any other mode in causing the Jahn-Teller distortions. Such a low-frequency vibrational mode is characteristic of nanosized molecular systems, being analogous to acoustic mode of phonon in solid. We find that such a vibrational mode plays an important role in the Jahn-Teller distortions as the ring size of annulene becomes large from benzene to [30]annulene. We also study the H/D isotope effect and find that the vibronic coupling constant of the E2g mode of 1513 cm-1 becomes larger by substituting deuteriums for hydrogens in negatively charged [30]annulene.
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U2 - 10.1016/S0301-0104(99)00226-8
DO - 10.1016/S0301-0104(99)00226-8
M3 - Article
AN - SCOPUS:0033416611
SN - 0301-0104
VL - 247
SP - 375
EP - 386
JO - Chemical Physics
JF - Chemical Physics
IS - 3
ER -