Physical Chemistry 3: — Chemical Kinetics — - Christian-Albrechts ...

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12.4 Radiationless processes in photoexcited molecules 253 • The reaction is thus thermally forbidden because of the high energy barrier at the avoided crossing between the trans and cis isomers on the left and right. • The reaction is photochemically allowed because of the barrierless adiabatic correlation between the ∗ states on the left and right. I Figure 12.7: Cis-trans isomerization of C 2 H 4 : Transformation of the and ∗ orbitals. Photochemical cis-trans isomerization of C 2 H 4 Traditional picture: Diabatic potentials diabatic crossing Topics in Chemical Kinetics and Dynamics • © F. Temps, IPC Kiel 35 I Figure 12.8: Cis-trans isomerization of C 2 H 4 : HMO picture with an avoided crossing. Photochemical cis-trans isomerization of C 2 H 4 Traditional picture: Avoided crossing avoided crossing Topics in Chemical Kinetics and Dynamics • © F. Temps, IPC Kiel 36
12.4 Radiationless processes in photoexcited molecules 254 I Figure 12.9: Internal coordinates relevant for the cis-trans isomerization of C 2 H 4 .The out-of-plane bending angle plays a role as coupling mode leading to a CI; the angles and play a role in the isomerization to H 3 CCH (also by a CI). Photochemical cis-trans isomerization of C 2 H 4 Important internal coordinates: Torsion Out-of-plane bend Barbatti et al., 2004 Physical Chemistry III: Chemical Kinetics • © F. Temps, IPC Kiel 258 I Figure 12.10: Diabatic model PES’s for C 2 H 4 . Photochemical cis-trans isomerization of C 2 H 4 Diabatic PES: (s1)-dimensional crossing seem Physical Chemistry III: Chemical Kinetics • © F. Temps, IPC Kiel 259
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Physical Chemistry 3: — Chemical
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iii 2.7 Temperature dependence of r
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v 7.1.2 Formal kinetic model 149 7.
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vii 12 Photochemical reactions 241
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ix Preface This scriptum contains l
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xi Disclaimer Use of this text is e
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xiii I Figure 2: Organisational mat
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xv I Figure 6: Recommended textbook
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1.2 Time scales for chemical reacti
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1.2 Time scales for chemical reacti
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1.3 Historical events 6 I Empirical
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1.4 References 8 2. Formal kinetics
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2.1 Definitions and conventions 10
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2.2 Kinetics of irreversible first-
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2.2 Kinetics of irreversible first-
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2.3 Kinetics of reversible first-or
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2.3 Kinetics of reversible first-or
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2.4 Kinetics of second-order reacti
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2.4 Kinetics of second-order reacti
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2.5 Kinetics of third-order reactio
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2.6 Kinetics of simple composite re
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2.7 Temperature dependence of rate
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3.1 Determination of the order of a
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3.2 Application of the steady-state
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3.2 Application of the steady-state
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3.4 Generalized first-order kinetic
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3.5 Numerical integration 58 I Surv
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3.5 Numerical integration 60 2 ord
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3.5 Numerical integration 62 3.5.5
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3.5 Numerical integration 64 , Func
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3.6 Oscillating reactions* 66 3.6 O
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3.6 Oscillating reactions* 68 • B
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3.6 Oscillating reactions* 70 (5) S
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3.6 Oscillating reactions* 72 I Fig
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3.6 Oscillating reactions* 74 [X]
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3.7 References 76 4. Experimental m
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4.3 The discharge flow (DF) techniq
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4.3 The discharge flow (DF) techniq
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4.4 Flash photolysis (FP) 82 4.4 Fl
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4.4 Flash photolysis (FP) 84 I Figu
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4.6 Stopped flow studies 86 4.6 Sto
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4.8 Relaxation methods 88 4.8 Relax
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4.9 Femtosecond spectroscopy 90 I F
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4.9 Femtosecond spectroscopy 92 I F
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4.10 References 94 5. Collision the
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5.1 Hardspherecollisiontheory 96
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5.1 Hardspherecollisiontheory 98 I
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5.1 Hard sphere collision theory 10
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5.2 Kinetic gas theory 102 I The 1D
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5.2 Kinetic gas theory 104 I Figure
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5.2 Kinetic gas theory 106 5.2.2 Th
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5.2 Kinetic gas theory 108 • Resu
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5.3 Transport processes in gases 11
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5.4 Advanced collision theory 116 W
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5.4 Advanced collision theory 118 I
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5.4 Advanced collision theory 120 5
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5.4 Advanced collision theory 126 a
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5.4 Advanced collision theory 130 (
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5.4 Advanced collision theory 136
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5.4 Advanced collision theory 138 6
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6.2 Polyatomic molecules 140 I Figu
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6.2 Polyatomic molecules 142 I Mode
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6.3 Trajectory Calculations 144 •
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6.3 Trajectory Calculations 146 7.
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7.1 Foundations of transition state
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7.2 Applications of transition stat
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7.3 Thermodynamic interpretation of
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7.4 Transition state spectroscopy 1
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8.1 Experimental observations 176 (
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8.2 Lindemann mechanism 178 8.2 Lin
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8.2 Lindemann mechanism 180 I Half-
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8.3 Generalized Lindemann-Hinshelwo
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8.4 The specific unimolecular react
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8.5 Collisional energy transfer* 20
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Page 277 and 278: Appendix B 262 Appendix A: Useful p
Page 279 and 280: Appendix B 264 The Marquardt-Levenb
Page 281 and 282: Appendix C 266 • Convolution of t
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Page 289 and 290: Appendix D 274 D.2 Special matrices
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Page 301 and 302: Appendix E 286 Appendix E: Laplace
Page 303 and 304: Appendix F 288 Appendix F: The Gamm
Page 305 and 306: Appendix G 290 Appendix G: Ergebnis
Page 307 and 308: Appendix G 292 I Anschauliche Bedeu
Page 309 and 310: Appendix G 294 Ergebnis: = 1 X
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Appendix G 304 G.8 Zustandssumme f
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Appendix G 306 G.9 Zustandssumme f
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Physical Chemistry 3: — Chemical Kinetics — - Christian-Albrechts ...

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