在本篇論文中，我們利用飛秒激發-探測光游離-光裂解技術研究MNA (N-methyl-1,2,3,4-tetrahydronaphthalen-2-amine)與MPBA (methyl(4-phenylbutyl)amine)陽離子激發態的緩解動態學過程。我們使用波長266 nm的飛秒雷射，以1 + 1共振增強多光子游離技術將MNA及MPBA分子的苯環端局部游離，再根據實驗需求以波長798、771或399 nm的飛秒雷射作為探測脈衝，以偵測陽離子由D1 state緩解至D0 state動態學過程。我們以連續動力學模型擬合兩分子的離子損耗瞬時訊號並得到三個時間常數。我們指認τ1為陽離子在D1 state的初始分子內振動能重新分配過程；τ2為陽離子從D1 state緩解至D0 state的電荷轉移過程(τCT)，其中MNA及MPBA離子的電荷轉移時間常數分別約為9.0及6.6 ps；而τ3為陽離子緩解至D0 state後的構型轉換再平衡過程。為了支持我們對2之指認，我們以相同技術研究無電荷轉移反應的PPN(3-phenylpropionitrile)陽離子，結果並沒有觀察到上述2時間量級的緩解過程，這強力支持了我們對2為電荷轉移時間常數之指認。另外，我們以理論計算估算兩分子的構型分佈及平均苯環中心至氮原子直線距離(Rave)，並結合本論文與實驗室前人對一系列類似離子系統的實驗結果，發現電荷轉移反應速率與Rave的關係概略符合指數衰減趨勢。

In this thesis, we employed femtosecond pump-probe photoionization-photofragmentation technique to study the relaxation dynamics of N-Methyl-1,2,3,4-tetrahydronaphthalen-2-amine (MNA) and Methyl(4-phenylbutyl)amine (MPBA) cations. These molecules are ionized by femtosecond pump pulse at 266 nm through 1+1 resonance-enhanced multiphoton ionization to locally ionize their phenyl group. Depending on specific experimental conditions, femtosecond probe pulses at 798, 771 or 399 nm were used to probe the relaxation dynamic from cationic D1 state to D0 state. We used a consecutive reaction kinetics model to fit the ion depletion transients, and we obtained three time constants. We assigned τ1 to the initial intramolecular vibrational energy redistribution occurring in the initially ionized D1 state. τ2 was assigned to the charge transfer in the cations from the D1 state to D0 state, and it was found to be about 9.0 and 6.6 ps for MNA and MPBA ions, respectively. Lastly, τ3 was assigned to the re-equilibrium process among all conformers in the D0 state. To support our assignment regarding τ2, we also studied 3-phenylpropionitrile (PPN) cation, a system in which charge transfer is expected to be energetically impossible, using the same technique. The results showed no relaxation dynamics in the similar time scale to the above-mentioned 2. This fact strongly supports our assignment of τ2 being related to the ionic charge transfer. In addition, we performed theoretical calculations to estimate conformational distributions and the average straight-line distance between the center of the phenyl ring and the nitrogen atom of the amine group (Rave). Combining results presented in this thesis and those reported by former group members of our laboratory, we found that the dependence of charge-transfer rate on Rave roughly conforms with an exponential decay relation.

1.Barber, J.; Andersson, B., Revealing the blueprint of
photosynthesis. Nature 1994, 370 (6484), 31-34.
2.Scholes, G. D.; Fleming, G. R.; Olaya-Castro, A.; Van Grondelle,
R., Lessons from nature about solar light harvesting. Nat. Chem.
2011, 3 (10), 763-774.
3.Lyu, S.; Farré, Y.; Ducasse, L.; Pellegrin, Y.; Toupance, T.;
Olivier, C.; Odobel, F., Push–pull ruthenium diacetylide complexes:
new dyes for p-type dye-sensitized solar cells. RSC Adv. 2016, 6
(24), 19928-19936.
4.Shin, H.; Kim, B. M.; Jang, T.; Kim, K. M.; Roh, D. H.; Nam, J.
S.; Kim, J. S.; Kim, U. Y.; Lee, B.; Pang, Y., Surface state‐
mediated charge transfer of Cs2SnI6 and its application in dye‐
sensitized solar cells. Adv. Energy Mater. 2019, 9 (3), 1803243.
5.Schlag, E. W.; Sheu, S. Y.; Yang, D. Y.; Selzle, H. L.; Lin, S.
H., Distal charge transport in peptides. Angew. Chem., Int. Ed.
2007, 46 (18), 3196-3210.
6.Shah, A.; Adhikari, B.; Martic, S.; Munir, A.; Shahzad, S.;
Ahmad, K.; Kraatz, H.-B., Electron transfer in peptides. Chem. Soc.
Rev. 2015, 44 (4), 1015-1027.
7.Yu, J.; Horsley, J. R.; Moore, K. E.; Shapter, J. G.; Abell, A.
D., The effect of a macrocyclic constraint on electron transfer in
helical peptides: a step towards tunable molecular wires. Chem.
Commun. 2014, 50 (14), 1652-1654.
8.Kawai, K.; Majima, T., Hole transfer kinetics of DNA. Acc. Chem.
Res. 2013, 46 (11), 2616-2625.
9.Meggers, E.; Michel-Beyerle, M. E.; Giese, B., Sequence dependent
long range hole transport in DNA. J. Am. Chem. Soc. 1998, 120 (49),
12950-12955.
10.Isied, S. S.; Ogawa, M. Y.; Wishart, J. F., Peptide-mediated
intramolecular electron transfer: long-range distance dependence.
Chem. Rev. 1992, 92 (3), 381-394.
11.Adams, D. M.; Brus, L.; Chidsey, C. E.; Creager, S.; Creutz,
C.; Kagan, C. R.; Kamat, P. V.; Lieberman, M.; Lindsay, S.;
Marcus, R. A., Charge transfer on the nanoscale: current status. J.
Phys. Chem. B 2003, 107 (28), 6668-6697.
12.Gilbert, M.; Albinsson, B., Photoinduced charge and energy transfer
in molecular wires. Chem. Soc. Rev. 2015, 44 (4), 845-862.
13.Lewis, F. D.; Letsinger, R. L.; Wasielewski, M. R., Dynamics of
photoinduced charge transfer and hole transport in synthetic DNA
hairpins. Acc. Chem. Res. 2001, 34 (2), 159-170.
14.Davis, W. B.; Svec, W. A.; Ratner, M. A.; Wasielewski, M. R.,
Molecular-wire behaviour in p-phenylenevinylene oligomers. Nature
1998, 396 (6706), 60-63.
15.Bixon, M.; Jortner, J.; Cortes, J.; Heitele, H.; Michel-Beyerle,
M., Energy gap law for nonradiative and radiative charge transfer
in isolated and in solvated supermolecules. J. Phys. Chem. 1994, 98
(30), 7289-7299.
16.Jortner, J.; Bixon, M.; Wegewijs, B.; Verhoeven, J. W.;
Rettschnick, R. P., Long-range, photoinduced charge separation in
solvent-free donor—bridge—acceptor molecules. Chem. Phys. Lett.
1993, 205 (4-5), 451-455.
17.Weinkauf, R.; Schanen, P.; Yang, D.; Soukara, S.; Schlag, E.,
Elementary processes in peptides: electron mobility and
dissociation in peptide cations in the gas phase. J. Phys. Chem.
1995, 99 (28), 11255-11265.
18.鄭博元 Conference in Memory of the Nobel Laureate Ahmed Zewail 演講
之投影片; 2018.
19.Weinkauf, R.; Lehr, L.; Metsala, A., Local ionization in 2-
phenylethyl-N, N-dimethylamine: charge transfer and dissociation
directly after ionization. J. Phys. Chem. A 2003, 107 (16), 2787-
2799.
20.Lehr, L.; Horneff, T.; Weinkauf, R.; Schlag, E., Femtosecond
dynamics after ionization: 2-phenylethyl-N, N-dimethylamine as a
model system for nonresonant downhill charge transfer in peptides.
J. Phys. Chem. A 2005, 109 (36), 8074-8080.
21.Sun, S.; Bernstein, E., Spectroscopy of neurotransmitters and their
clusters. 1. Evidence for five molecular conformers of
phenethylamine in a supersonic jet expansion. J. Am. Chem. Soc.
1996, 118 (21), 5086-5095.
22.Li, S.; Bernstien, E.; Seeman, J., Stable conformations of
benzylamine and N, N-dimethylbenzylamine. J. Phys. Chem. 1992, 96
(22), 8808-8813.
23.Law, K.; Bernstein, E., Molecular jet study of van der waals
complexes of flexible molecules: n‐propyl benzene solvated by small
alkanesa. J. Chem. Phys. 1985, 82 (7), 2856-2866.
24.Sun, S.; Mignolet, B.; Fan, L.; Li, W.; Levine, R. D.; Remacle,
F., Nuclear motion driven ultrafast photodissociative charge
transfer of the penna cation: an experimental and computational
study. J. Phys. Chem. A 2017, 121 (7), 1442-1447.
25.宋桓宇. 氣相超快光游離誘發雙官能基陽離子內之電荷轉移動態學研究. 國立清華
大學碩士論文, 2018.
26.楊博竣. 超快光游離誘發2-苯基乙基-N,N-二甲基胺陽離子內之電荷轉移動態學研
究. 國立清華大學碩士論文, 2017.
27.Closs, G.; Calcaterra, L.; Green, N.; Penfield, K.; Miller, J.,
Distance, stereoelectronic effects, and the Marcus inverted region
in intramolecular electron transfer in organic radical anions. J.
Phys. Chem. 1986, 90 (16), 3673-3683.
28.Closs, G. L.; Miller, J. R., Intramolecular long-distance electron
transfer in organic molecules. Science 1988, 240 (4851), 440-447.
29.Johnson, M. D.; Miller, J. R.; Green, N. S.; Closs, G. L.,
Distance dependence of intramolecular hole and electron transfer in
organic radical ions. J. Phys. Chem. 1989, 93 (4), 1173-1176.
30.顏暐儒. 光游離誘發雙官能基陽離子超快電荷轉移動態學之距離相依性研究. 國立
清華大學碩士論文, 2019.
31.涂宸瑄. 以超快時間解析光分解光譜研究光游離誘發雙官能基陽離子電荷轉移動態
學. 國立清華大學碩士論文, 2020.
32.Diedhiou, M.; West, B. J.; Bouwman, J.; Mayer, P. M., Ion
Dissociation Dynamics of 1, 2, 3, 4-Tetrahydronaphthalene: Tetralin
as a Test Case For Hydrogenated Polycyclic Aromatic Hydrocarbons.
J. Phys. Chem. A. 2019, 123 (51), 10885-10892.
33.Selim, E. T.; Helal, A., The study of C1 C3 monosubstituted alkyl
benzenes by the inverse convolution of first differential
ionization efficiency curves. Org. Mass Spectrom. 1982, 17 (11),
539-543.
34.Staley, R. H.; Kleckner, J. E.; Beauchamp, J., Relationship
between orbital ionization energies and molecular properties.
Proton affinities and photoelectron spectra of nitriles. J. Am.
Chem. Soc. 1976, 98 (8), 2081-2085.
35.Frisch, M.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.;
Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.;
Mennucci, B.; Petersson, G., Gaussian 09, revision D. 01. Gaussian,
Inc., Wallingford CT: 2009.
36.Burns, L. A.; Mayagoitia, Á. V.-.; Sumpter, B. G.; Sherrill, C.
D., Density-functional approaches to noncovalent interactions: A
comparison of dispersion corrections (DFT-D), exchange-hole dipole
moment (XDM) theory, and specialized functionals. J. Chem. Phys.
2011, 134 (8), 084107.
37.Chai, J.-D.; Head-Gordon, M., Long-range corrected hybrid density
functionals with damped atom–atom dispersion corrections. Phys.
Chem. Chem. Phys. 2008, 10 (44), 6615-6620.
38.Li, A.; Muddana, H. S.; Gilson, M. K., Quantum mechanical
calculation of noncovalent interactions: a large-scale evaluation
of PMx, DFT, and SAPT approaches. J. Chem. Theory Comput. 2014, 10
(4), 1563-1575.
39.Amirav, A.; Even, U.; Jortner, J., Cooling of large and heavy
molecules in seeded supersonic beams. Chem. Phys. 1980, 51 (1-2),
31-42.
40.Johnson, W. S.; Bauer, V. J.; Margrave, J. L.; Frisch, M. A.;
Dreger, L. H.; Hubbard, W. N., The energy difference between the
chair and boat forms of cyclohexane. the twist conformation of
cyclohexane. J. Am. Chem. Soc. 1961, 83 (3), 606-614.