臺灣博碩士論文加值系統

In this Thesis, the author presents unprecedentedly detailed studies on the structure and dynamics of ionic and neutral transient species that are of crucial importance in molecular photovoltaic devices, using nanosecond time-resolved near/mid-IR spectroscopy with the help of density functional theory (DFT) calculations and chemometrics techniques. The author has investigated (1) the back electron transfer (BET) dynamics in photoinduced intermolecular electron transfer reaction between pyrene (Py) and 1,4-dicyanobenzene (DCB) in acetonitrile and (2) the structure of the lowest excited triplet (T1) state of p-nitroaniline (PNA) in acetonitrile-d3. In the first work, the transient near/mid-IR spectra of Py radical dimer cation and DCB radical anion are observed in the nano- to microsecond (ns–μs) time regime after photoexcitation of Py. Global fitting analysis of the time-resolved IR data reveals a dual role of acetonitrile as solvent and “charge mediator” of the charge recombination between Py radical dimer cation and DCB radical anion in the BET reaction. This finding may have implications for dye-sensitized solar cells because acetonitrile is a commonly used solvent for redox couples in these types of devices. In the second work, the transient mid-IR spectra of PNA in the T1 state generated after photoexcitation of PNA and subsequent intersystem crossing are examined to characterize the structure of T1 PNA. Comparison of the experimental IR spectra with DFT calculated results on explicitly solvated PNA shows that T1 PNA has a partial quinoid structure, which sharply contrasts with the well-known zwitterionic charge-transfer structure of the lowest excited singlet state of PNA. The studies presented in this Thesis not only illustrate the applicability of the time-resolved near/mid-IR method to a wide variety of important photophysical and photochemical processes in the condensed phase, but they also provide otherwise hardly obtainable insights into the structure and dynamics of transient species (radicals and excited-state molecules) involved in charger transfer processes.

In this Thesis, the author presents unprecedentedly detailed studies on the structure and dynamics of ionic and neutral transient species that are of crucial importance in molecular photovoltaic devices, using nanosecond time-resolved near/mid-IR spectroscopy with the help of density functional theory (DFT) calculations and chemometrics techniques. The author has investigated (1) the back electron transfer (BET) dynamics in photoinduced intermolecular electron transfer reaction between pyrene (Py) and 1,4-dicyanobenzene (DCB) in acetonitrile and (2) the structure of the lowest excited triplet (T1) state of p-nitroaniline (PNA) in acetonitrile-d3. In the first work, the transient near/mid-IR spectra of Py radical dimer cation and DCB radical anion are observed in the nano- to microsecond (ns–μs) time regime after photoexcitation of Py. Global fitting analysis of the time-resolved IR data reveals a dual role of acetonitrile as solvent and “charge mediator” of the charge recombination between Py radical dimer cation and DCB radical anion in the BET reaction. This finding may have implications for dye-sensitized solar cells because acetonitrile is a commonly used solvent for redox couples in these types of devices. In the second work, the transient mid-IR spectra of PNA in the T1 state generated after photoexcitation of PNA and subsequent intersystem crossing are examined to characterize the structure of T1 PNA. Comparison of the experimental IR spectra with DFT calculated results on explicitly solvated PNA shows that T1 PNA has a partial quinoid structure, which sharply contrasts with the well-known zwitterionic charge-transfer structure of the lowest excited singlet state of PNA. The studies presented in this Thesis not only illustrate the applicability of the time-resolved near/mid-IR method to a wide variety of important photophysical and photochemical processes in the condensed phase, but they also provide otherwise hardly obtainable insights into the structure and dynamics of transient species (radicals and excited-state molecules) involved in charger transfer processes.

Abstract i
Acknowledgements iii
Table of Contents v
List of Figures vi
List of Tables ix
List of Schemes ix
Chapter I Introduction 1
Chapter II Nanosecond Time-resolved Near/Mid-IR spectrometer and Data Analysis Techniques 5
II-1 Introduction 6
II-2 Nanosecond Time-resolved Dispersive IR Spectrometer 6
II-2.1 TRIR Setup 7
II-2.2 Sample Circulation System 10
II-3 Singular Value Decomposition Analysis 11
II-3.1 Mathematical Definition 11
II-4 Global Fitting Analysis 12
Chapter III BET Mechanism of a Bimolecular PET Reaction between Py and DCB 15
III-1 Introduction 16
III-2 Materials and Methods 18
III-2.1 Materials 18
III-2.2 Nanosecond Time-resolved Near/Mid-IR Spectroscopy 18
III-2.3 Computational Details 19
III-3 Results and Discussion 19
III-3.1 Nanosecond TRNIR/MIR Spectra of Py and DCB in ACN Solution Measured under Ar Bubbling. 19
III-3.2 Vibrational Assignments 20
III-3.3 Molecular Oxygen Quenching Experiment 22
III-3.4 Kinetic Analysis 23
III-3.5 Concentration Dependence Studies of the BET Reaction between Py and DCB in ACN Solution 27
III-3.6 TRIR Spectra of Py and DCB in Benzene Solution 28
III-4 Summary 29
Chapter IV Structural Elucidation on the T1 State of PNA in CD3CN Solution 30
IV-1 Introduction 31
IV-2 Materials and Methods 32
IV-2.1 Sample Preparation Methods 32
IV-2.2 Nanosecond Time-Resolved Infrared Spectroscopy 33
IV-2.3 Computational Details 34
IV-3 Results and Discussion 34
IV-3.1 Nanosecond TRIR Spectra of PNA in CD3CN under Ar Environment 34
IV-3.2 SVD analysis of the TRIR Spectra of PNA in CD3CN 36
IV-3.3 TRIR Spectra of PNA in CD3CN under O2 Environment 37
IV-3.4 Experimental IR Spectra of the T1 State of PNA and Its Isotopomers 39
IV-3.5 Calculated IR spectra of the T1 State of PNA and Its Isotopomers 42
IV-4 Structural of T1 PNA 46
IV-5 Summary 48
Chapter V Conclusions and Future Prospects 49
References 51

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