1 Introduction |
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1 | (18) |
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1 | (1) |
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1.2 Gas-Surface Interactions |
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2 | (3) |
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1.3 Gas-Surface Reaction Dynamics |
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5 | (4) |
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1.4 Steric Effects in Gas-Surface Reactions |
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9 | (2) |
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1.5 Inspiration From Gas-Phase Experiments |
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11 | (4) |
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15 | (1) |
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16 | (3) |
2 Experimental Setup |
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19 | (32) |
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2.1 Overview of Experimental Setup |
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19 | (1) |
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2.2 Molecular Beam Source |
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19 | (2) |
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2.3 Surface Science UHV Chamber |
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21 | (7) |
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21 | (1) |
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2.3.2 Quadrupole Mass Spectrometer (QMS) |
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22 | (3) |
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25 | (1) |
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25 | (2) |
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27 | (1) |
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2.4 CW-IR State-Preparation Setup |
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28 | (5) |
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28 | (1) |
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29 | (2) |
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31 | (1) |
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2.4.4 Tunable λ/2 Wave Plate |
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32 | (1) |
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2.5 Frequency Stabilization |
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33 | (12) |
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2.5.1 Lamb Dip Detection and Characterization |
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36 | (4) |
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40 | (5) |
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2.6 Pyroelectric Detection of Vibrationally Excited Molecules in a Molecular Beam |
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45 | (4) |
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49 | (2) |
3 State Specific Preparation and Alignment of Gas-Phase Reagents |
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51 | (44) |
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51 | (1) |
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3.2 Rovibrational Excitation of Molecular Beam |
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51 | (27) |
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3.2.1 Rapid Adiabatic Passage (RAP) |
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52 | (26) |
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3.3 Alignment of Vibrationally Excited Molecules in the Laboratory Frame |
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78 | (14) |
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3.3.1 Angular Momentum Alignment |
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79 | (7) |
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3.3.2 Vibrational Transition Dipole Moment Alignment |
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86 | (6) |
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92 | (3) |
4 State-Resolved Steric Effects in Methane Chemisorption on Ni(100) |
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95 | (38) |
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95 | (1) |
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4.2 CH4(v3 = 1) Reactivity and Alignment Effects on Ni(100) |
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95 | (20) |
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4.2.1 Independence of Excitation Efficiency Upon Polarization Rotation |
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98 | (1) |
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4.2.2 Polarization Dependence of Vibrationally Excited Methane Reactivity |
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99 | (4) |
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4.2.3 Effect of Hyperfine Depolarization on CH4(v3)-R(0) Reactivity |
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103 | (3) |
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4.2.4 Comparison of lair, and Calculated Alignment Coefficients for CH4(v3) |
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106 | (2) |
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4.2.5 Detailed Polarization Angle Dependence of the CH4(v3)-R(0) Reactivity |
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108 | (2) |
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4.2.6 Absolute Sticking Coefficients of CH4(v3)-R(0) on Ni(100) |
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110 | (5) |
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4.3 CD3H(vi = 1) Reactivity and Alignment Effects on Ni(100) |
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115 | (6) |
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4.3.1 Effect of Hyperfine Depolarization on CD3H(v1)-R(0) |
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117 | (1) |
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4.3.2 Comparison of Δp and Calculated Alignment Coefficients for CD3H(v1) |
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118 | (1) |
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4.3.3 Effect of Polarization Rotation with Respect to the Surface for CD3H(v1)-R(0) |
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119 | (2) |
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4.4 Discussion of Results |
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121 | (8) |
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129 | (4) |
5 State-Resolved Steric Effects in CH4(v3) Dissociation on Ni(11O) |
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133 | (14) |
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133 | (2) |
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5.2 CH4(v3) on Ni(110)-(Parallel vs. Normal) |
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135 | (5) |
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5.3 CH4(v3) on Ni(110)-(Perpendicular vs. Normal) |
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140 | (2) |
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5.4 Discussion of Results |
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142 | (4) |
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146 | (1) |
6 Summary and Outlook |
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147 | (14) |
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147 | (4) |
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6.2 Experimental Improvements |
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151 | (7) |
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6.2.1 Modulation of Excitation Laser Polarization |
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151 | (2) |
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6.2.2 Free-Swinging UHV Pendulum for Molecular Beam Chopping |
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153 | (5) |
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158 | (1) |
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159 | (2) |
Appendix A: Procedure for 'Locking' OPO Idler Frequency to Lamb Dip |
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161 | (6) |
Appendix B: Beta Axis Calculation for R(0), R(1), P(1), Q(1) With and Without K-Resolution |
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167 | (6) |
Appendix C: CD3H(v1) Rovibrational Transitions |
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173 | |