Хімія, фізика та технологія поверхні, 2015, 6 (1), 42-55.

Синглет-триплетне розщеплення етилену при взаємодії з поверхнею Cu(100) і малими кластерами міді



DOI: https://doi.org/10.15407/hftp06.01.042

S. V. Bondarchuk, B. F. Minaev

Анотація


На основі теорії функціоналу густини досліджено комплекси етилену з атомом Купруму, кластером Cu2 та поверхнею Cu(100). Показано, що етилен виявляє три основних типи зв’язування: моно-π, моно-σ та ди-σ. З поверхнею міді етилен утворює моно-π-зв’язаний комплекс. При цьому висота над поверхнею (hads) і енергія (Eads) адсорбції складають 2.23 Å і 0.47 еВ відповідно. З атомом Купруму у основному стані утворюється комплекс симетрії 2A', що відповідає синглетному етилену. Для оптимізації геометрії комплексу триплетного етилену розроблена розрахункова процедура, що включає змішування граничних орбіталей. Отриманий стійкий комплекс 2B2 лежить на 0.47 еВ вище комплексу 2A'. Дана енергія приписана синглет-триплетному збудженню етилену при взаємодії з міддю, а сам комплекс 2B2 може бути отриманий в умовах термічної активації.

Ключові слова


триплетні π-нуклеофіли; комплекси мідь-етилен; модель Дьюара-Чата-Дункансона; DFT; QTAIM

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Посилання


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DOI: https://doi.org/10.15407/hftp06.01.042

Copyright (©) 2015 S. V. Bondarchuk, B. F. Minaev