Melvin B. Robin's Higher Excited States of Polyatomic Molecules PDF

By Melvin B. Robin

ISBN-10: 0125899025

ISBN-13: 9780125899024

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A d d i t i o n a l , more direct confirmation c o m e s f r o m t h e p h o t o e l e c t r o n s p e c t r a -1[ B 5 9 ] , w h i c h s h o w t h e h i g h e s t s i g m a o r b i t a l i n e t h y l e n e t o b e 15 7 0 0 c m below t h e o c c u p i e d- 1 p i M O , w h e r e a s in c y c l o p r o p e n e , t h i s d i f f e r e n c e is r e d u c e d t o 9 7 0 0 c m . T h e 3 6 ι σ —> 1 α π * e x c i t a t i o n i n c y c l o p r o p e n e is t h e olefin 2 a n a l o g of t h e n —» ττ* e x c i t a t i o n of t h e i s o e l e c t r o n i c m o l e c u l e diazirine ( S e c t i o n I V .

From this, and the TWO-CENTER appropriate UNSATURATES empirical correction for substituent effects, o n e c a n e s t i m a t e w h e r e π - > 3 p a n d π - » 3 d t r a n s i t i o n s w i l l fall, t h u s f a c i l i t a t i n g t h e t a s k of s p e c t r a l a s s i g n m e n t . I n l i n e w i t h t h i s , w e feel confident that the Rydberg 27 0 0 0 - 2 2 000, 22 0 0 0 - 1 8 000, a n d transitions 1 in olefins with terms of 14 0 0 0 - 1 2 0 0 0 c m " , h a v e 3 s , 3 p , a n d 3d u p p e r states, respectively.

I n f a c t , j u s t t h i s vibrational frequency is e x c i t e d in t h e p h o t o e l e c t r o n s p e c t r a of olefins F i g . I V . A - 1 4 . D e t a i l s of t h e Ν —» R ( 3 s ) and Ν —» V absorptions of several alkyl olefins in the gas phase. T h e molar e x t i n c t i o n coefficients for the v a r i o u s curves can b e o b t a i n e d b y m u l t i p l y i n g t h e optical d e n s i t y b y t h e factors g i v e n i n parentheses [W18L 88 IV. , ? 2 0 42 44 46 48 I . I . I . I 50 52 54 56 58 FREQUENCY, cm" 1 42 3 44 46 48 50 52 54 56 58 Χ 10 F i g .

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Higher Excited States of Polyatomic Molecules by Melvin B. Robin


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