caa a22 4500 605487650 CHVBK 20210128100451.0 cr unu---uuuuu 210128e20150301xx s 000 0 eng 10.1007/s00214-015-1633-7 doi (NATIONALLICENCE)springer-10.1007/s00214-015-1633-7 Why does deuterium substitution lead to the contraction of X···π distance? Origin of the reverse Ubbelohde effect in XH···π interaction [Elektronische Daten] [Taro Udagawa, Masanori Tachikawa] The H/D/T geometrical isotope effect (GIE) on XH···π interaction in XH···benzene (X=CH3, OH, and NH2) complexes is analyzed by MP2 level of multi-component molecular orbital calculations, which can take account of nuclear quantum nature. The distances between X atom and center of the benzene ring in XD···benzene and XT···benzene complexes are found to be shorter than that in XH···benzene complex, which shows a different trend in the conventional hydrogen-bonded complexes. Such reverse Ubbelohde effect in XH···benzene complexes is explained by the cooperative effect of two kinds of GIEs: (1) primary GIE on the covalent X-H bond and (2) secondary GIE on the H···π distance. We have clearly revealed that the primary GIE is dominant in the GIE of XH···π complexes. Springer-Verlag Berlin Heidelberg, 2015 Geometrical isotope effect (GIE) nationallicence XH···π interaction nationallicence Ubbelohde effect nationallicence Multi-component molecular orbital calculation nationallicence Nuclear quantum nature nationallicence Udagawa Taro Department of Chemistry and Biomolecular Science, Faculty of Engineering, Gifu University, Yanagido 1-1, 501-1193, Gifu, Japan aut Tachikawa Masanori Quantum Chemistry Division, Graduate School of Science, Yokohama City University, Seto 22-2, Kanazawa-ku, 236-0027, Yokohama, Japan aut Theoretical Chemistry Accounts Springer Berlin Heidelberg 134/3(2015-03-01), 1-5 1432-881X 134:3<1 2015 134 214 https://doi.org/10.1007/s00214-015-1633-7 text/html Onlinezugriff via DOI BK010053 XK010053 XK010000 Metadata rights reserved Springer special CC-BY-NC licence nationallicence 1 research-article jats NATIONALLICENCE NATIONALLICENCE NL-springer NATIONALLICENCE 856 40 https://doi.org/10.1007/s00214-015-1633-7 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Udagawa Taro Department of Chemistry and Biomolecular Science, Faculty of Engineering, Gifu University, Yanagido 1-1, 501-1193, Gifu, Japan aut NATIONALLICENCE 700 1- Tachikawa Masanori Quantum Chemistry Division, Graduate School of Science, Yokohama City University, Seto 22-2, Kanazawa-ku, 236-0027, Yokohama, Japan aut NATIONALLICENCE 773 0- Theoretical Chemistry Accounts Springer Berlin Heidelberg 134/3(2015-03-01), 1-5 1432-881X 134:3<1 2015 134 214