Probing the vibrational spectroscopy of the deprotonated thymine radical by photodetachment and state-selective autodetachment photoelectron spectroscopy.

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Presentation transcript:

Probing the vibrational spectroscopy of the deprotonated thymine radical by photodetachment and state-selective autodetachment photoelectron spectroscopy via dipole bound states Dao-Ling Huang, Guo-Zhu Zhu, Lai-Sheng Wang, Department of Chemistry, Brown University, Providence, RI 71th International Symposium on Molecular Spectroscopy University of Illinois at Champaign-Urbana Jun 20-24, 2016

Radiation damage of DNA Primary impact of high energy quanta Radiation damage, i.e., strand break UV, X-ray, etc Secondary particles, i.e., ions, radicals, low-energy electrons Interactions of low-energy electrons with DNA Top-down Bottom up Single DNA constituents: isolated base, the sugar and the phosphate units B. Boudaïffa, P. Cloutier, D. Hunting, M. A. Huels, L. Sanche, Science 2000, 287, 1658 B. D. Michael, P. O'Neill, Science 2000, 287, 1603 P. Swiderek, Angew. Chem., Int. Ed. 2006, 45, 4056

Previous studies on thymine Dissociative electron attachment Electron affinities calculations 3.2-3.4 eV 3.7-4.5 eV Low-energy (<2 eV) electrons – loss H L. T. M. Profeta, et al, Mol. Phys., 2003, 101, 3277–3284 S. Denifl, et al, J. Phys. Chem. A, 2004, 108, 6562–6569 S. Ptasinska, et al, J. Chem. Phys., 2005, 123, 124302 D. S. Jiao and H. Y. Wang, Mol. Phys., 2008, 106, 2653–2665 E. C. M. Chen, et al, Nucleosides, Nucleotides Nucleic Acids, 2008, 27, 506–524 H. Abdoul-Carime, S. Gohlke, E. Illenberger, Phys. Rev. Lett. 2004, 92, 168103 S. Ptasińska, et al, Phys. Rev. Lett. 2005, 95, 093201 P. Swiderek, Angew. Chem., Int. Ed. 2006, 45, 4056 Anion photoelectron spectroscopy EA = 3.250 ± 0.015 eV B. F. Parsons, S. M. Sheehan, T. A. Yen, D. M. Neumark, N. Wehres and R. Weinkauf, Phys. Chem. Chem. Phys., 2007, 9, 3291–3297

Photodetachment and autodetachment photoelectron spectroscopy 3.2-3.4 eV 3.7-4.5 eV 355 nm (3.496 eV)

Principle of photoelectron spectroscopy and autodetachment Franck-Condon principle BE = hv - KE M Binding energy v=2 e- KE v=1 v=0 hv M- ADE Configuration coordinate

Principle of photoelectron spectroscopy and autodetachment Franck-Condon principle Neutral molecule, m > 2.5 D dipole bound state BE = hv - KE e- M (M-) *DBS Binding energy v=2 v'=2 e- KE Autodetachment v=1 v'=1 phenoxide anion, radical μ = 4.0 D v=0 v'=0 Δν = -1 hv M- ADE Configuration coordinate J. Simons, J. Am. Chem. Soc. 1981, 103, 3971

Principle of photoelectron spectroscopy and autodetachment Franck-Condon principle Neutral molecule, m > 2.5 D dipole bound state Non-Franck-Condon BE = hv - KE e- M (M-) *DBS Binding energy v=2 v'=2 Binding energy e- KE Autodetachment v=1 v'=1 v=0 v'=0 Δν = -1 hv M- ADE Autodetachment can resonantly enhance the intensity. Configuration coordinate J. Simons, J. Am. Chem. Soc. 1981, 103, 3971

Experimental set-up thymine+NaOH CH3OH/H2O L. S. Wang, J. Chem. Phys. 2015, 143, 040901

Non-resonant photoelectron image and spectrum Mode Symmetry Theo. (cm-1) v1 A″ 70 v2 93 v3 135 v4 262 v5 A′ 285 v6 388 v7 397 v8 450 v9 555 v10 608 v11 670 v12 720 v13 727 [N1-H] ● B3LYP/6-311++G(d,p) Cs symmetry Peak BE (cm-1) Shift (cm-1) Assignment 000 26322(5) A 26604(5) 282 501 B 26715(5) 393 701 C 26884(25) 562 901 D 27044(22) 722 1201 E 27267(18) 945 701901 F 27422(16) 1100 902 G 27593(14) 1271 9011201 H 27784(12) 1462 701902 I 27873(12) 1551 5019011201 J 27963(10) 1641 903 K 27983(10) 1661 7019011201 L 28024(8) 1702 5011202 M 28135(5) 1813 9021201 EA = 3.2635 ± 0.0006 eV (by resonant PES)

Photodetachment spectrum threshold BEDBS = 238 ± 5 cm-1

Resonant photoelectron spectra and images threshold

Comparison between non-resonant and resonant spectra

Comparison between non-resonant and resonant spectra

Assignments of dipole-bound states Resonant Energy level diagram

Assignments of dipole-bound states Energy level diagram

Assignments of Franck-Condon inactive peaks Mode Symmetry Theo. (cm-1) v1 A″ 70 v2 93 v3 135 v4 262 v5 A′ 285 v6 388 v7 397 v8 450 v9 555 v10 608 v11 670 v12 720 v13 727 [N1-H] radical B3LYP/6-311++G(d,p) Cs symmetry Peak BE (cm-1) Shift (cm-1) Assignment 000 26322(5) A 26604(5) 282 501 B 26715(5) 393 701 C 26884(25) 562 901 D 27044(22) 722 1201 E 27267(18) 945 701901 … a 26396(8) 74 101 b 26413(5) 91 201 c 26462(5) 140 301 d 26482(5) 160 101201 e 26526(5) 204 101301 f 26582(5) 260 401 g 26644(8) 321 101401 h 26678(5) 356 201401

Summary Accurately determined the electron affinity of N1[T-H]● to be 3.2635 ± 0.0006 eV and the binding energy of dipole-bound ground state to be 238 ± 5 cm-1; Highly non-Franck-Condon resonant-enhanced photoelectron spectra were obtained due to state-selective vibrational autodetachment via dipole-bound states; Obtained 11 fundamental vibrational frequencies in the low-frequencies regime.

Acknowledgement Prof. Lai-Sheng Wang Dr. Dao-Ling Huang other group members

Assignments of dipole-bound states Non-resonant Resonant Energy level diagram

Assignments of dipole-bound states

Assignments of dipole-bound states

Assignments of dipole-bound states

Assignments of dipole-bound states

Assignments of dipole-bound states

Assignments of dipole-bound states

Assignments of dipole-bound states

Assignments of dipole-bound states Non-resonant Resonant Energy level diagram

Non-resonant photoelectron image and spectrum