A variety of laser spectroscopic methods are employed in this thesis research for studies of CF3N... more A variety of laser spectroscopic methods are employed in this thesis research for studies of CF3NO, an interesting model photodissociative system, and for investigation of low energy rotations and vibrations of small molecules and low molecular weight clusters in free jet expansions. Nonradiative energy decay for electronically excited CF3NO is investigated in an argon matrix. By comparing the visible absorption spectrum with pulsed laser photoacoustic and fluorescence excitation spectra it is argued that all nonradiative decay processes are fast, thus eliminating the likelihood of transient separation of CF3 and NO photofragments in the matrix cage or appreciable decay through a low lying triplet state. No evidence is found for a "channel two" decay mechanism in the matrix in contrast to gas phase work of others. Upper state vibrational relaxation is seen to be exceedingly fast by From his excellent example I have managed to learn a little about the value of careful, patient, and persistent work. His enthusiasm, optimism and willingness to attempt new or difficult projects have managed, with time, to even temper my own conservative nature. I would like to thank the technical staff in the chemistry department for their vital support during my work at Oregon State University. These people include John Archibald, Robert Boyer, Gerald Allison, and Doyle Woodrow without whom this research would never have been taken to completion. A number of other people have assisted me greatly in the lab, most notably Nancy Triggs, Steven Bares, George Pubanz, and Jeng Yang. I am indebted to each of them for their generous participation. Finally my heartfelt thanks goes out to my wife, Sena, and our children, Mary, Jessica and Bridget, for their patience and support during the many years I spent obtaining both my undergraduate and graduate degrees. TABLE OF CONTENTS CHAPTER 1 INTRODUCTION The use of lasers in chemical physics CF3NO Spectroscopy and Photophysics CHAPTER 2 4 PHOTOACOUSTIC SPECTROSCOPY AND ENERGY RELAXATION IN MATRIX Jet Expansion into a Finite Background Pressure 92
In einer elektrochemischen Zelle mit 0.1 M K-phosphat + 0.05 M Na-borat (pH 8) wurde eine Fe-Elek... more In einer elektrochemischen Zelle mit 0.1 M K-phosphat + 0.05 M Na-borat (pH 8) wurde eine Fe-Elektrode mit dem zerhackten Lichtstrahl (80 Hz) eines Ar-Ionen-Lasers bestrahlt. Die durch die thermischen Änderungen im Fe induzierten periodischen Druckschwankungen wurden mit einem piezoelektrischen Detektor analysiert. Potentiodynamische und coulostatische Messungen zeigen eine bei -0.8 V (SCE) beginnende Fe3O4-Bedeckung der Fe-Oberfl äche. γ-Fe2O3 bildet sich auf Fe3O4 bei -0.4 V. Bei der galvanostatischen Reduktion des passiven Fe wird die vollst ändige Reduktion von γ-Fe2O3 durch Änderungen in den akustischen Signalen angezeigt.
Most laboratory exercises in molecular spectroscopy focus on the information gained from the freq... more Most laboratory exercises in molecular spectroscopy focus on the information gained from the frequencies, rather than the intensities, of spectral lines. In contrast, we describe here a laboratory exercise that illustrates the principles of calculating and measuring the relative intensities of spectral bands. Specifically, the intensity of the first infrared overtone band of nitric oxide is compared to the intensitv of the nitric oxide fundamental band. The results of the measurements are compared with a simplified theorv in which the anharmonic contributions of the vibrationai wave functions are used to calculate the necessary transition-moment integrals, and thus to predict the relative intensities of the two hands.
A variety of laser spectroscopic methods are employed in this thesis research for studies of CF3N... more A variety of laser spectroscopic methods are employed in this thesis research for studies of CF3NO, an interesting model photodissociative system, and for investigation of low energy rotations and vibrations of small molecules and low molecular weight clusters in free jet expansions. Nonradiative energy decay for electronically excited CF3NO is investigated in an argon matrix. By comparing the visible absorption spectrum with pulsed laser photoacoustic and fluorescence excitation spectra it is argued that all nonradiative decay processes are fast, thus eliminating the likelihood of transient separation of CF3 and NO photofragments in the matrix cage or appreciable decay through a low lying triplet state. No evidence is found for a "channel two" decay mechanism in the matrix in contrast to gas phase work of others. Upper state vibrational relaxation is seen to be exceedingly fast by From his excellent example I have managed to learn a little about the value of careful, patient, and persistent work. His enthusiasm, optimism and willingness to attempt new or difficult projects have managed, with time, to even temper my own conservative nature. I would like to thank the technical staff in the chemistry department for their vital support during my work at Oregon State University. These people include John Archibald, Robert Boyer, Gerald Allison, and Doyle Woodrow without whom this research would never have been taken to completion. A number of other people have assisted me greatly in the lab, most notably Nancy Triggs, Steven Bares, George Pubanz, and Jeng Yang. I am indebted to each of them for their generous participation. Finally my heartfelt thanks goes out to my wife, Sena, and our children, Mary, Jessica and Bridget, for their patience and support during the many years I spent obtaining both my undergraduate and graduate degrees. TABLE OF CONTENTS CHAPTER 1 INTRODUCTION The use of lasers in chemical physics CF3NO Spectroscopy and Photophysics CHAPTER 2 4 PHOTOACOUSTIC SPECTROSCOPY AND ENERGY RELAXATION IN MATRIX Jet Expansion into a Finite Background Pressure 92
Epitaxial single crystal GaN films (2.0 μtm thick) were implanted 60° off the <0001> surfac... more Epitaxial single crystal GaN films (2.0 μtm thick) were implanted 60° off the <0001> surface normal with 600 keV O+ ions at 190 or 210 K over a range of ion fluences from 4.8x 1017 to 5.0 × 1020 ions/m2. The implantation damage, as determined by in-situ Rutherford Backscattering Spectrometry in a…
The relative reactivities of six polycyclic iodomethylarenes toward reduction by triphenyltin hyd... more The relative reactivities of six polycyclic iodomethylarenes toward reduction by triphenyltin hydride in deuterobenzene at 70°C have been obtained. While a limited range of reactivities is observed, a trend does exist. Data are best correlated with calculated energy differences between transition states, based on adding an electron to the antibonding carbon-iodine orbitals, and parent arenes. These results agree with those obtained from substituent effect and isotope effect studies on other organic iodides which apparently undergo electron transfer with trialkyl or triaryltin radicals. *Dedicated to Prof. M. J. S. Dewar on the occasion of his 70th birthday.
Colloidal suspensions of Li, Na, K, Rb and Cs were prepared in diethyl ether. The effective sizes... more Colloidal suspensions of Li, Na, K, Rb and Cs were prepared in diethyl ether. The effective sizes of particle aggregates were estimated by comparison of experimental visible extinction spectra with calculated spectra using the full equations of Mie scattering. The extinction spectra of Cs sols demonstrate unusual blue shifting as particle aggregation proceeds. The blue-shifted band is assigned to tbe transverse resonance of a linear string of Cs particles. Surface-enhanced Raman (SER) spectra are reported for Na, K and Rb sols. Observation of an OH stretching band (3585 cm-') on the Na sol and growth of the SER bands as moisture is introduced to the Na and K sols strongly suggest that the bands derive from alkali metal hydroxides on the metal surfaces. When a trace of D,O is present in the Na sol a new SER band at 2640 cm-' is observed, and is assigned to the OD stretch of surface NaOD. The Raman excitation spectrum for the 290 cm-' SER band on Na is compared with the extinction band of the Na sol. The result is found to be in good qualitative agreement with the electromagnetic theory of surfaceenhanced Raman scattering.
Most laboratory exercises in molecular spectroscopy focus on the information gained from the freq... more Most laboratory exercises in molecular spectroscopy focus on the information gained from the frequencies, rather than the intensities, of spectral lines. In contrast, we describe here a laboratory exercise that illustrates the principles of calculating and measuring the relative intensities of spectral bands. Specifically, the intensity of the first infrared overtone band of nitric oxide is compared to the intensitv of the nitric oxide fundamental band. The results of the measurements are compared with a simplified theorv in which the anharmonic contributions of the vibrationai wave functions are used to calculate the necessary transition-moment integrals, and thus to predict the relative intensities of the two hands.
A variety of laser spectroscopic methods are employed in this thesis research for studies of CF3N... more A variety of laser spectroscopic methods are employed in this thesis research for studies of CF3NO, an interesting model photodissociative system, and for investigation of low energy rotations and vibrations of small molecules and low molecular weight clusters in free jet expansions. Nonradiative energy decay for electronically excited CF3NO is investigated in an argon matrix. By comparing the visible absorption spectrum with pulsed laser photoacoustic and fluorescence excitation spectra it is argued that all nonradiative decay processes are fast, thus eliminating the likelihood of transient separation of CF3 and NO photofragments in the matrix cage or appreciable decay through a low lying triplet state. No evidence is found for a "channel two" decay mechanism in the matrix in contrast to gas phase work of others. Upper state vibrational relaxation is seen to be exceedingly fast by From his excellent example I have managed to learn a little about the value of careful, patient, and persistent work. His enthusiasm, optimism and willingness to attempt new or difficult projects have managed, with time, to even temper my own conservative nature. I would like to thank the technical staff in the chemistry department for their vital support during my work at Oregon State University. These people include John Archibald, Robert Boyer, Gerald Allison, and Doyle Woodrow without whom this research would never have been taken to completion. A number of other people have assisted me greatly in the lab, most notably Nancy Triggs, Steven Bares, George Pubanz, and Jeng Yang. I am indebted to each of them for their generous participation. Finally my heartfelt thanks goes out to my wife, Sena, and our children, Mary, Jessica and Bridget, for their patience and support during the many years I spent obtaining both my undergraduate and graduate degrees. TABLE OF CONTENTS CHAPTER 1 INTRODUCTION The use of lasers in chemical physics CF3NO Spectroscopy and Photophysics CHAPTER 2 4 PHOTOACOUSTIC SPECTROSCOPY AND ENERGY RELAXATION IN MATRIX Jet Expansion into a Finite Background Pressure 92
In einer elektrochemischen Zelle mit 0.1 M K-phosphat + 0.05 M Na-borat (pH 8) wurde eine Fe-Elek... more In einer elektrochemischen Zelle mit 0.1 M K-phosphat + 0.05 M Na-borat (pH 8) wurde eine Fe-Elektrode mit dem zerhackten Lichtstrahl (80 Hz) eines Ar-Ionen-Lasers bestrahlt. Die durch die thermischen Änderungen im Fe induzierten periodischen Druckschwankungen wurden mit einem piezoelektrischen Detektor analysiert. Potentiodynamische und coulostatische Messungen zeigen eine bei -0.8 V (SCE) beginnende Fe3O4-Bedeckung der Fe-Oberfl äche. γ-Fe2O3 bildet sich auf Fe3O4 bei -0.4 V. Bei der galvanostatischen Reduktion des passiven Fe wird die vollst ändige Reduktion von γ-Fe2O3 durch Änderungen in den akustischen Signalen angezeigt.
Most laboratory exercises in molecular spectroscopy focus on the information gained from the freq... more Most laboratory exercises in molecular spectroscopy focus on the information gained from the frequencies, rather than the intensities, of spectral lines. In contrast, we describe here a laboratory exercise that illustrates the principles of calculating and measuring the relative intensities of spectral bands. Specifically, the intensity of the first infrared overtone band of nitric oxide is compared to the intensitv of the nitric oxide fundamental band. The results of the measurements are compared with a simplified theorv in which the anharmonic contributions of the vibrationai wave functions are used to calculate the necessary transition-moment integrals, and thus to predict the relative intensities of the two hands.
A variety of laser spectroscopic methods are employed in this thesis research for studies of CF3N... more A variety of laser spectroscopic methods are employed in this thesis research for studies of CF3NO, an interesting model photodissociative system, and for investigation of low energy rotations and vibrations of small molecules and low molecular weight clusters in free jet expansions. Nonradiative energy decay for electronically excited CF3NO is investigated in an argon matrix. By comparing the visible absorption spectrum with pulsed laser photoacoustic and fluorescence excitation spectra it is argued that all nonradiative decay processes are fast, thus eliminating the likelihood of transient separation of CF3 and NO photofragments in the matrix cage or appreciable decay through a low lying triplet state. No evidence is found for a "channel two" decay mechanism in the matrix in contrast to gas phase work of others. Upper state vibrational relaxation is seen to be exceedingly fast by From his excellent example I have managed to learn a little about the value of careful, patient, and persistent work. His enthusiasm, optimism and willingness to attempt new or difficult projects have managed, with time, to even temper my own conservative nature. I would like to thank the technical staff in the chemistry department for their vital support during my work at Oregon State University. These people include John Archibald, Robert Boyer, Gerald Allison, and Doyle Woodrow without whom this research would never have been taken to completion. A number of other people have assisted me greatly in the lab, most notably Nancy Triggs, Steven Bares, George Pubanz, and Jeng Yang. I am indebted to each of them for their generous participation. Finally my heartfelt thanks goes out to my wife, Sena, and our children, Mary, Jessica and Bridget, for their patience and support during the many years I spent obtaining both my undergraduate and graduate degrees. TABLE OF CONTENTS CHAPTER 1 INTRODUCTION The use of lasers in chemical physics CF3NO Spectroscopy and Photophysics CHAPTER 2 4 PHOTOACOUSTIC SPECTROSCOPY AND ENERGY RELAXATION IN MATRIX Jet Expansion into a Finite Background Pressure 92
Epitaxial single crystal GaN films (2.0 μtm thick) were implanted 60° off the <0001> surfac... more Epitaxial single crystal GaN films (2.0 μtm thick) were implanted 60° off the <0001> surface normal with 600 keV O+ ions at 190 or 210 K over a range of ion fluences from 4.8x 1017 to 5.0 × 1020 ions/m2. The implantation damage, as determined by in-situ Rutherford Backscattering Spectrometry in a…
The relative reactivities of six polycyclic iodomethylarenes toward reduction by triphenyltin hyd... more The relative reactivities of six polycyclic iodomethylarenes toward reduction by triphenyltin hydride in deuterobenzene at 70°C have been obtained. While a limited range of reactivities is observed, a trend does exist. Data are best correlated with calculated energy differences between transition states, based on adding an electron to the antibonding carbon-iodine orbitals, and parent arenes. These results agree with those obtained from substituent effect and isotope effect studies on other organic iodides which apparently undergo electron transfer with trialkyl or triaryltin radicals. *Dedicated to Prof. M. J. S. Dewar on the occasion of his 70th birthday.
Colloidal suspensions of Li, Na, K, Rb and Cs were prepared in diethyl ether. The effective sizes... more Colloidal suspensions of Li, Na, K, Rb and Cs were prepared in diethyl ether. The effective sizes of particle aggregates were estimated by comparison of experimental visible extinction spectra with calculated spectra using the full equations of Mie scattering. The extinction spectra of Cs sols demonstrate unusual blue shifting as particle aggregation proceeds. The blue-shifted band is assigned to tbe transverse resonance of a linear string of Cs particles. Surface-enhanced Raman (SER) spectra are reported for Na, K and Rb sols. Observation of an OH stretching band (3585 cm-') on the Na sol and growth of the SER bands as moisture is introduced to the Na and K sols strongly suggest that the bands derive from alkali metal hydroxides on the metal surfaces. When a trace of D,O is present in the Na sol a new SER band at 2640 cm-' is observed, and is assigned to the OD stretch of surface NaOD. The Raman excitation spectrum for the 290 cm-' SER band on Na is compared with the extinction band of the Na sol. The result is found to be in good qualitative agreement with the electromagnetic theory of surfaceenhanced Raman scattering.
Most laboratory exercises in molecular spectroscopy focus on the information gained from the freq... more Most laboratory exercises in molecular spectroscopy focus on the information gained from the frequencies, rather than the intensities, of spectral lines. In contrast, we describe here a laboratory exercise that illustrates the principles of calculating and measuring the relative intensities of spectral bands. Specifically, the intensity of the first infrared overtone band of nitric oxide is compared to the intensitv of the nitric oxide fundamental band. The results of the measurements are compared with a simplified theorv in which the anharmonic contributions of the vibrationai wave functions are used to calculate the necessary transition-moment integrals, and thus to predict the relative intensities of the two hands.
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