(The) photodissociation and photoionization dynamics of methylamine = 메틸아민의 광분해 및 광이온화 동역학 연구

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The photodissociation and photoionization dynamics of methylamines on the first electronically excited state has been investigated using the velocity map imaging technique. In photodissociation, two distinct velocity components are found in the H(D) translational energy distribution, implying the existence of two different reaction pathways for the bond dissociation. The high H(D) velocity component with the small internal energy of the radical fragment is ascribed to the N-H(D) fragmentation via the coupling of $S_1$ to the upper-lying $S_2$ repulsive potential energy surface along the N-H(D) bond elongation axis. Dissociation on the ground $S_0$ state prepared via the nonadiabatic dynamics at the conical intersection should be responsible for the slow H(D) fragment. The branching ratio of the fast and slow components is found to be sensitive to the initial vibronic state for the N-H bond dissociation of $CH_3NH_2$, whereas it is little affected in the N-D dissociation event of $CD_3ND_2$. The fast component is found to be more dominant in the translational distribution of D from $CD_3ND_2$ than it is in that of H from $CH_3NH_2$. The experimental result is discussed with a plausible mechanism of the conical intersection dynamics. The photoionization dynamics of methylamine ($CH_3NH_2$, $CH_3ND_2$ and $CH_3NHD$) via vibrational state selected $\Atilde$ state was also investigated with REMPI-Photoelecton imaging experiment. The initially given vibration in the intermediate was conserved in the cation and it became maximum kinetic energy peak which is the most intensive. The intensive progress of $ν_{sym}$ band was appeared in electron kinetic energy distribution. From a Frank-Condon analysis, this is originated from the elongation of N-H(N-D) bond. The isotope exchange identified main peaks in photoelectron spectrum. The observed Photoelectron angular distribution showed that reduced $β_2$ parameter and significant contribution of $β_4$ parameter. We found o...
Advisors
Kim, Sang-Kyuresearcher김상규researcher
Description
한국과학기술원 : 화학과,
Publisher
한국과학기술원
Issue Date
2009
Identifier
327810/325007  / 020055090
Language
eng
Description

학위논문(박사) - 한국과학기술원 : 화학과, 2009. 8., [ xii, 110 p. ]

Keywords

methylamine; dynamics; photodissociation; photoionization; laser; 메틸아민; 동역학; 광분해; 광이온화; 레이져; methylamine; dynamics; photodissociation; photoionization; laser; 메틸아민; 동역학; 광분해; 광이온화; 레이져

URI
http://hdl.handle.net/10203/31735
Link
http://library.kaist.ac.kr/search/detail/view.do?bibCtrlNo=327810&flag=dissertation
Appears in Collection
CH-Theses_Ph.D.(박사논문)
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