University of Pittsburgh Alessandro Cembran Jiali Gao University of Minnesota Charge redistribution in the β naphthol water complex as measured by high resolution Stark spectroscopy ID: 1026147
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1. Adam J. FleisherDavid W. PrattUniversity of PittsburghAlessandro CembranJiali GaoUniversity of MinnesotaCharge redistribution in theβ-naphthol-water complex as measured by high resolution Stark spectroscopy in the gas phase.MG-04
2. Condensed phase H-bondsS0S1S2RO-HRO– + H+?LECTFig. 5 in Schütz, M., Bürgi, T., Leutwyler, S., Fischer, T. J. Chem. Phys. 99, 1469, (1993).In the gas phase, the cis-2HN-water origin is red shifted by 371 cm-1 from the 2HN origin.cm-1
3. Fleisher, A.J., Morgan, P.J., Pratt, D.W. J. Chem. Phys. 131, 211101, (2009).Gas phase H-bonds2-HN-water
4. Field free 2HN-water (TA-03)BASimExp2.1 cm-12140 MHz
5. Stark cell and collection optics
6. 30901.430904.7 cm-1 0.04 cm-10 V/cm846 V/cm1776 V/cmStark effect in 2-naphtholFleisher, A.J., Morgan, P.J., Pratt, D.W. J. Chem. Phys. 131, 211101, (2009).
7. 2-HN-water Stark spectra2 cm-10 V/cm169 V/cm846 V/cm
8. 2HN-water Stark splitting0 V/cm169 V/cm846 V/cm0.04 cm-1
9. Results State Bare Molecule H2O NH3 Ground 1.01 D 4.00 D 3.89 DExcited 1.17 D 4.66 D 4.94 D
10. In 2HN-H2O,Q = 0.07 e in S0, and Q* = 0.10 e in S1Dipole decompositionFleisher, A.J., Morgan, P.J., Pratt, D.W. J. Chem. Phys. 131, 211101, (2009).
11. This results in a 323 cm-1 calculated red shift (371 cm-1 in experiment).Static vector modelsolutesolventinducedcharge transfer
12. BLW-ED methodScheme 1 in Mo, Y., Gao, J., Peyerimhoff, S.D. J. Chem. Phys., 112, 5530 (2000).BLW-ED reported using B3LYP/6-31+G* (geometries were optimized using M06-2X/6-31+G*).S0c2HNA(cm-1)BLW|%|static|%|c2HNW(cm-1)BLW|%|static|%|ΔEr+420?ΔEstat-7302015??22ΔEpol-980275??14ΔEct-19005380??64ΔEint-3200?ammonia, waterβ-naphthol
13. Dynamic charge distributionHF/6-31+G* optimization of 11 points along a path exchanging the two hydrogen atoms of water.
14. Dynamic charge distributionStartTransition State
15. Induced charge motion… produces a large change in the charge distribution of the molecule to which it is attached.Motion of the water molecular along the torsional coordinate …Motion of the ammonia molecular along the torsional coordinate …… produces little change in the charge distribution of the molecule to which it is attached.HF/6-31+G* optimization of points along a path exchanging equivalent solvent hydrogens.
16. Induced charge motion
17. Time-varying dipole field (II)
18. A static model of energy and dipole moment decomposition based on electrostatic contributions was used to explain the experimentally observed red shift in 2HNW.The block-localized wavefunction energy decomposition (BLW-ED) method was used to investigate electrostatic, induced, and charge transfer interactions.Future work on understanding the importance of the time varying nature of the water dipole must be included.Important to the understanding of condensed phase water systems.Summary
19. Justin YoungPhilip MorganDiane Miller Marquette UniversityRyan BirdJessica ThomasCasey ClementsPatrick WalshAcknowledgmentsDr. David W. Pratt University of Pittsburgh Dr. David Plusquellic NIST, jb95 developmentDr. David Borst Intel, Stark development
20.
21. Time-varying dipole field (I)Torsional TS was optimized using HF/6-31+G*, along with 8 other points between ϕ = 0 – 180°.The electric potential at the COM of 2HNW as a function of the torsional coordinate ϕ was fit to 21 data points.The electric potential function was scaled by the probability of water being in each position along ϕ using the experimental V2 = 206 cm-1, compared to a barrierless torsion.aaRazavy, M. and Pimpale, A. Physics Reports, 168, 305 (1988).
22. H-bond ‘jumps’ in bulk waterFig. 1 in Ji, M., Odelius, M., Gaffney, K.J. Science. 328, 1003, (2010).
23. Fleisher, A.J., Morgan, P.J., Pratt, D.W. J. Chem. Phys. 131, 211101, (2009).Excited State Proton Transfer
24. S0S1µ1 (D)1.011.17µ2 (D)1.4721.472µind (D)0.290.36Eµµ (cm-1)-62.4-113.6Eαµ (cm-1)-23.6-43.5ECT (cm-1)-427.7-958.0Ecomplex,rel (cm-1)-513.7-1115.1Red Shift in 2HNA
25. S0S1µ1 (D)1.011.17µ2 (D)1.8551.855µind (D)0.650.75Eµµ (cm-1)-61.2-147.4Eαµ (cm-1)-40.5-52.3ECT (cm-1)-183.2-408.2Ecomplex,rel (cm-1)-284.9-607.9Red Shift in 2HNW
26. 0.04 cm-130315.430318.6 cm-1 EA0 V/cm1269 V/cm423 V/cmStark Effect in 2-Naphthol-Ammonia
27. Vector Model – 2HNA
28. 2HNW Field Free DataA (σ = 0)B (σ = 1)S0A (MHz)1725.9(1)1724.9(1)B (MHz)548.1(1)548.1(1)C (MHz)416.6(1)416.8(1)ΔI (amu Å2)-1.781-2.609S1A (MHz)1687.4(1)1686.3(1)B (MHz)553.4(1)553.3(1)C (MHz)417.3(1)417.5(1)ΔI (amu Å2)-1.741-2.648Origin (MHz)915333681(30)915339355(30)# lines141458OMC (MHz)4.15.0L/G LW (MHz)9/259/25Rel. Intensity13A (σ = 0)B (σ = 1)S0ΔJ (KHz)0.17(9)0.03(3)ΔJK (KHz)-0.8(7)-1.0(2)ΔK (KHz)3(2)1.2(4)δJ (KHz)0.04(4)0.005(14)δK (KHz)5(2)1.5(5)S1ΔJ (KHz)0.20(9)-0.04(3)ΔJK (KHz)-1.2(6)-0.4(2)ΔK (KHz)3(2)0.6(4)δJ (KHz)0.05(5)-0.02(1)δK (KHz)5(2)1.1(5)OMC (MHz)3.74.3Watson A-reduction distortion terms improve the fit of J ≥ 20 transitions, and do not change any other inertial parameters by more than two standard deviations.
29. 2HNW dipole projectionsS0S1μa (D)-3.11-4.09μb (D)2.512.23μc (D)0.00.0μ (D)4.004.66