Adam J. Fleisher David W. Pratt University of Pittsburgh Alessandro Cembran Jiali Gao University of Minnesota Charge redistribution in the β-naphthol-water.

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Presentation transcript:

Adam J. Fleisher David W. Pratt 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 in the gas phase. MG-04

Condensed phase H-bonds S0S0 S1S1 S2S2 RO-HRO – + H + ? LECT Fig. 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

Fleisher, A.J., Morgan, P.J., Pratt, D.W. J. Chem. Phys. 131, , (2009). Gas phase H-bonds 2-HN-water

Field free 2HN-water (TA-03) B A Sim Exp 2.1 cm MHz

Stark cell and collection optics

cm cm -1 0 V/cm 846 V/cm 1776 V/cm Stark effect in 2-naphthol Fleisher, A.J., Morgan, P.J., Pratt, D.W. J. Chem. Phys. 131, , (2009).

2-HN-water Stark spectra 2 cm -1 0 V/cm 169 V/cm 846 V/cm

2HN-water Stark splitting 0 V/cm 169 V/cm 846 V/cm 0.04 cm -1

Results State Bare Molecule H 2 O NH 3 Ground 1.01 D 4.00 D 3.89 D Excited 1.17 D 4.66 D 4.94 D

In 2HN-H 2 O, Q = 0.07 e in S 0, and Q * = 0.10 e in S 1 Dipole decomposition Fleisher, A.J., Morgan, P.J., Pratt, D.W. J. Chem. Phys. 131, , (2009).

This results in a 323 cm -1 calculated red shift (371 cm -1 in experiment). Static vector model solute solvent induced charge transfer

BLW-ED method Scheme 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*). S0S0 c2HNA (cm -1 ) BLW |%| static |%| c2HNW (cm -1 ) BLW |%| static |%| ΔErΔEr +420? ΔE stat ??22 ΔE pol ??14 ΔE ct ??64 ΔE int -3200? ammonia, water β-naphthol

Dynamic charge distribution HF/6-31+G* optimization of 11 points along a path exchanging the two hydrogen atoms of water.

Dynamic charge distribution Start Transition State

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.

Induced charge motion

Time-varying dipole field (II)

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

Justin Young Philip Morgan Diane Miller Marquette University Ryan Bird Jessica Thomas Casey Clements Patrick Walsh Acknowledgments Dr. David W. Pratt University of Pittsburgh Dr. David Plusquellic NIST,jb95 development Dr. David Borst Intel, Stark development

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 V 2 = 206 cm -1, compared to a barrierless torsion. a a Razavy, M. and Pimpale, A. Physics Reports, 168, 305 (1988).

H-bond ‘jumps’ in bulk water Fig. 1 in Ji, M., Odelius, M., Gaffney, K.J. Science. 328, 1003, (2010).

Fleisher, A.J., Morgan, P.J., Pratt, D.W. J. Chem. Phys. 131, , (2009). Excited State Proton Transfer

S0S0 S1S1 µ 1 (D) µ 2 (D)1.472 µ ind (D) E µµ (cm -1 ) E αµ (cm -1 ) E CT (cm -1 ) E complex,rel (cm -1 ) Red Shift in 2HNA

S0S0 S1S1 µ 1 (D) µ 2 (D)1.855 µ ind (D) E µµ (cm -1 ) E αµ (cm -1 ) E CT (cm -1 ) E complex,rel (cm -1 ) Red Shift in 2HNW

0.04 cm cm -1 E A 0 V/cm 1269 V/cm 423 V/cm Stark Effect in 2-Naphthol-Ammonia

Vector Model – 2HNA

2HNW Field Free Data A (σ = 0)B (σ = 1) S0S0 A (MHz)1725.9(1)1724.9(1) B (MHz)548.1(1) C (MHz)416.6(1)416.8(1) ΔI (amu Å 2 ) S1S1 A (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 Å 2 ) Origin (MHz) (30) (30) # lines OMC (MHz) L/G LW (MHz)9/25 Rel. Intensity13 A (σ = 0)B (σ = 1) S0S0 ΔJ (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) S1S1 ΔJ (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) Watson 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.

2HNW dipole projections S0S0 S1S1 μ a (D) μ b (D) μ c (D)0.0 μ (D)