A practical guide to magnetic circular dichroism spectroscopy:
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| 100 | 1 | |a Mason, W. Roy |e Verfasser |4 aut | |
| 245 | 1 | 0 | |a A practical guide to magnetic circular dichroism spectroscopy |c W. Roy Mason |
| 264 | 1 | |a Hoboken, NJ |b Wiley-Interscience |c 2007 | |
| 300 | |a XII, 223 S. |b graph. Darst. | ||
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| adam_text | Titel: A practical guide to magnetic circular dichroism spectroscopy
Autor: Mason, W. Roy
Jahr: 2007
CONTENTS
PREFACE xi
1. Introduction 1
2. Polarized Light 4
2.1. Linear Polarization and Plane Polarized Waves 4
2.2. Circular Polarization and Circularly Polarized Waves 5
2.3. Absorption Probabilities 10
3. Theoretical Framework: Definition of MCD Terms 14
3.1. Born-Oppenheimer/Franck-Condon Approximation 14
3.2. Rigid-Shift Approximation 16
3.3. Áé-, Bo-, and Co-Term Parameters 20
3.4. A Terms 20
3.5. C Terms 24
3.6. Â Terms 26
3.7. Pseudo A Terms: Overlapping  Terms 29
3.8. Overlapping C Terms 30
3.9. Ground-State Near Degeneracy 30
3.10. Deviation from the Linear Limit 31
3.11. Zeeman Splitting Bandwidth 32
3.12. Relative Magnitude of A, B, and C Terms 33
3.13. Parameter Evaluation. Lineshape Function 34
3.14. Parameter Evaluation. Method of Moments 34
4. Measurement of MCD Spectra 36
4.1. MCD Spectrometer 36
4.2. Detector Signals: Measurement of AA and A 38
4.3. Computer Control and Data Acquisition 40
4.4. Optical Elements and Stray Polarization Effects 41
4.5. Calibration 42
4.6. Magnet Systems 43
vi CONTENTS
5. The Interpretation of MCD Spectra 46
5.1. Term Assignments 46
5.2. Prediction of Sign and Approximate Magnitude of
MCD Terms 47
5.3. The Wigner-Eckart Theorem and Reduced
Matrix Elements (RMEs) 47
5.4. MCD-Term Equations Involving RMEs 48
5.5. Evaluation of RMEs for MCD Terms 51
5.6. Evaluation of Matrix Elements for LCAO-MO Functions 55
5.7. Spin-Orbit Coupling Considerations 57
5.8. Herzberg-Teller Approximation for Vibronic Transitions 59
6. Case Studies I. Diamagnetic Systems: A and  Terms 60
6.1. A and  Terms for Diamagnetic Atoms and Molecules 60
6.2. Atomic Mercury Vapor 61
6.3. The Sodide Ion Na~ in a Solid NH3 Matrix 63
6.4. Square Complexes of D4h Symmetry 64
6.4.1. Ligand Field Spectra for PtCl| 65
6.4.2. Intense Bands and Allowed Transitions for Square
Complexes 66
6.4.3. LMCT Transitions for Ñß×à and AuX^, X = CF,
Br ,I 67
6.4.4. MLCT Transitions for Pt(CN)^ 70
6.4.5. d -* ñ Transitions for Pt(NH3)i+ and Pt(en)!+ 73
6.5. Linear Two-Coordinate Dcoa Complexes 75
6.5.1. HgX2 and AuX? X = Cl , Br , and I~ 76
6.5.2. MLCT Transitions for Pt(PBu3)2 78
6.6. Octahedral Complexes 80
6.6.1. LMCT Transitions for nd6 Halide Complexes 80
6.6.2. LMCT Transitions for 4d10 Complexes SbCl? and
SnCir 80
6.6.3. Metal-Centered s - ñ and LMCT Transitions in
BiCir 82
6.6.4. MLCT and d -+ ñ Transitions for nd6 M(CO)6
and M(CN)e Complexes 84
6.7. Metal Cluster Complexes 86
6.7.1. MLCT Transitions for Triangular Pt3(CO)3(P(?-Bu)3)3 87
6.7.2. Metal-Centered Transitions in the Hg3(dppm)3+ Cluster
Complex 89
6.7.3. Pt — Au Framework and Intraframework Transitions
in the Gold Cluster Complexes Pt(AuPPh3)|+ and
Au(AuPPh3)i+ 93
CONTENTS vii
6.8. Triiodide Ion: An Example of a Pseudo A Term 97
6.9. Methyl Iodide: ? - s* and Iodine-Based 5p Rydberg
Transitions 99
6.9.1. ? —*¦ s* Transitions 100
6.9.2. Rydberg Transitions for CH3I and CD3I in the Vacuum
UV 100
6.10. Benzene: it - · ir* and Rydberg Transitions 103
6.10.1. -p -* ir* Transitions 103
6.10.2. Rydberg Transitions 108
6.11. D4/! Cyclobutadiene Dianion LI2[C4(Me3Si)4] 109
6.12. Zinc Phthalocyanine (Tetraazotetrabenzoporphyrin) Complex,
ZnPc(2-) 111
6.12.1. Vitreous Solution Spectra at Low Temperature 112
6.12.2. Matrix-Isolated ZnPc(2-) 113
6.13. Chlorophyll Q Band, An Example Using ? Terms 116
6.14. Surface Plasmon Band for Colloidal Gold Nanoparticles 119
7. Case Studies II. Paramagnetic Systems: C Terms 121
7.1. Paramagnetic Cyano Complexes 121
7.1.1. LMCT Transitions for Fe(CN)i~ 121
7.1.2. LMCT Spectra for M(CN)I~, M = Mo(V)
and W(V) 125
7.2. Ground-State Magnetization for Unstable Metallocenes 127
7.3. Determination of the Ground State for
Matrix-Isolated Manganese(II) Phthalocyanine from C Terms 129
7.4. Mononegative Cyclooctatetraene Ion (COT~) Matrix
Isolated in Argon 131
7.5. Ground-State Electronic and Structural
Information from Variable Temperature and Field Studies
of C Terms: Application to Non-Heme-Iron Enzymes 135
7.6. Modeling the Structure of the
Native Intermediate of the Multicopper Oxidase
from Rhus Vernicifera Lacease Isolated from the Japanese
Lacquer Tree 138
7.7. High-Spin Metal Centers with Ground-State
Spin 1/2; Application to the Protein-Oxidized
Rubredoxin, Desulfovibrio gigas 142
7.8. MCD of Co2+ as a Probe of Metal-Binding Sites in
E. coli Methionyl Aminopeptidase 146
7.9. Optically Detected Electron Paramagnetic
Resonance (ODEPR) by Microwave-Modulated
MCD: Application to the Optical Anisotropy of the
Blue Copper Protein Pseudomonas aeruginosa Azurin 150
viii CONTENTS
7.10. Single-Molecule Magnets (SMMs) 155
7.10.1. Spin Polarization in the S = 10 Mixed Valence
Mn(IV)-Mn(III) Cluster Complex
[Mn12O12(O2CR)16(H2O)4] 155
7.10.2. Single Ion and Cluster Spin in the
5 = 6 [Cr12O9(O2CCMe3)15] Cluster Complex 158
7.11. Lanthanide Ions in Crystalline Environments 162
7.11.1. Na3Ln(ODA)3 · 2NaC104 · 6H2O (LnODA,
Ln = Eu and Nd) 163
7.11.2. LiErF4, LiYF4/Eu3+, and KY3F1O/Eu3+Crystals 165
8. Magnetic Vibrational Circular Dichroism (MVCD) and X-Ray
Magnetic Circular Dichroism (XMCD) 171
8.1. MVCD 171
Instrumentation 172
Examples 173
MVCD for Metal Carbonyl Complexes M(CO)6,
M = Cr, Mo, and W 173
Rotationally Resolved MVCD for Carbon Monoxide 174
Rotationally Resolved MVCD for Methane 176
Rotationally Resolved MVCD for Acetylene and
Deuterated Isotopomers 176
8.2. XMCD 179
8.2.1. XMCD Measurements 179
8.2.2. Sum Rules 180
8.2.3. Magnetic Properties of GdNi2 Laves Phase 180
8.2.4. XMCD Study of Re 5d Magnetism in the Sr2CrReO6
Double Perovskite 181
8.2.5. XMCD Study of Mn(III) and Mn(IV) Magnetic
Contributions to the SMM [Mn12O)2(CH3CO2)16(H2O)24] ·
2CH3COOH · 4H2O 184
8.2.6. XMCD for Pseudomonas aeruginosa Nickel(II) Azurin
(NiAz) 187
9. Magnetic Linear Dichroism Spectroscopy 188
9.1. Introduction 188
9.2. MLD Terms and Term Parameters 188
9.3. Measurement of MLD Spectra 192
9.4. Some Examples of MLD Spectra 192
9.4.1. Atomic Mercury Vapor 193
9.4.2. Metal Atoms Isolated in Noble Gas Matrices 195
9.4.3. Lanthanide Metal Ions in Solution: Ho3+ 197
9.4.4. Ferrocytochrome c and Deoxymyoglobin 199
8. L.I.
8. 1.2.
8. L.3.
8. 1.4.
8. 1.5.
8. L.6.
CONTENTS
ix
APPENDIXES
Appendix A. Tables for the Symmetry Groups O and Td
202
Table A. 1. Function ø and Operator Op Transformation Coefficients for
Groups O and Td 202
Table A.2. 3/ , 2j, and 2jm Phases in the O and Td Bases for Single-Valued
Irreps 203
Table A.3. 3jm for O and Td Bases for Single-Valued Irreps 204
Table A.4. 6/ for O and Td Bases for Single-Valued Irreps 205
Appendix B. Tables for the Fourfold Symmetry Group D4 207
Table B.I. Function ø and Operator Op Transformation Coefficients for
Group D4 207
Table B.2. 3/ , 2j, and 2jm Phases in D4 Bases for Single-Valued
Irreps 207
Table B.3. 3jm in D4 Bases for Single-Valued Irreps 208
Table B.4. 6/ in D4 Bases for Single-Valued Irreps 208
Appendix C. Tables for the Threefold Symmetry Group D3 209
Table C. 1. Function ø and Operator Op Transformation Coefficients for
Group £ 3 209
Table C.2. 3/, 2j, and 2jm Phases in D3 Bases for Single-Valued
Irreps 209
Table C.3. 3jm in D3 Bases for Single-Valued Irreps 210
Table C.4. 6/ in D3 Bases for Single-Valued Irreps 210
Table D.I. Partial List of SO3 D O 3jm Factors
Appendix D. 3jm Factors for Single-Valued Irreps of the
SO3 D O and O D D4 Chains 211
at f bij O
Involving Single-Valued Irreps 211
Table D.2.. Partial List of O D D4 3jm Factors ( °l { , ) f*
a2 fi b2JD4
Involving Single-Valued Irreps 212
Reviews and References 213
Index
218
|
| adam_txt |
Titel: A practical guide to magnetic circular dichroism spectroscopy
Autor: Mason, W. Roy
Jahr: 2007
CONTENTS
PREFACE xi
1. Introduction 1
2. Polarized Light 4
2.1. Linear Polarization and Plane Polarized Waves 4
2.2. Circular Polarization and Circularly Polarized Waves 5
2.3. Absorption Probabilities 10
3. Theoretical Framework: Definition of MCD Terms 14
3.1. Born-Oppenheimer/Franck-Condon Approximation 14
3.2. Rigid-Shift Approximation 16
3.3. Áé-, Bo-, and Co-Term Parameters 20
3.4. A Terms 20
3.5. C Terms 24
3.6. Â Terms 26
3.7. Pseudo A Terms: Overlapping  Terms 29
3.8. Overlapping C Terms 30
3.9. Ground-State Near Degeneracy 30
3.10. Deviation from the Linear Limit 31
3.11. Zeeman Splitting Bandwidth 32
3.12. Relative Magnitude of A, B, and C Terms 33
3.13. Parameter Evaluation. Lineshape Function 34
3.14. Parameter Evaluation. Method of Moments 34
4. Measurement of MCD Spectra 36
4.1. MCD Spectrometer 36
4.2. Detector Signals: Measurement of AA and A 38
4.3. Computer Control and Data Acquisition 40
4.4. Optical Elements and Stray Polarization Effects 41
4.5. Calibration 42
4.6. Magnet Systems 43
vi CONTENTS
5. The Interpretation of MCD Spectra 46
5.1. Term Assignments 46
5.2. Prediction of Sign and Approximate Magnitude of
MCD Terms 47
5.3. The Wigner-Eckart Theorem and Reduced
Matrix Elements (RMEs) 47
5.4. MCD-Term Equations Involving RMEs 48
5.5. Evaluation of RMEs for MCD Terms 51
5.6. Evaluation of Matrix Elements for LCAO-MO Functions 55
5.7. Spin-Orbit Coupling Considerations 57
5.8. Herzberg-Teller Approximation for Vibronic Transitions 59
6. Case Studies I. Diamagnetic Systems: A and  Terms 60
6.1. A and  Terms for Diamagnetic Atoms and Molecules 60
6.2. Atomic Mercury Vapor 61
6.3. The Sodide Ion Na~ in a Solid NH3 Matrix 63
6.4. Square Complexes of D4h Symmetry 64
6.4.1. Ligand Field Spectra for PtCl|" 65
6.4.2. Intense Bands and Allowed Transitions for Square
Complexes 66
6.4.3. LMCT Transitions for Ñß×à and AuX^, X = CF,
Br",I" 67
6.4.4. MLCT Transitions for Pt(CN)^" 70
6.4.5. d -* ñ Transitions for Pt(NH3)i+ and Pt(en)!+ 73
6.5. Linear Two-Coordinate Dcoa Complexes 75
6.5.1. HgX2 and AuX?\ X = Cl", Br", and I~ 76
6.5.2. MLCT Transitions for Pt(PBu3)2 78
6.6. Octahedral Complexes 80
6.6.1. LMCT Transitions for nd6 Halide Complexes 80
6.6.2. LMCT Transitions for 4d10 Complexes SbCl?" and
SnCir 80
6.6.3. Metal-Centered s - ñ and LMCT Transitions in
BiCir 82
6.6.4. MLCT and d -+ ñ Transitions for nd6 M(CO)6
and M(CN)e" Complexes 84
6.7. Metal Cluster Complexes 86
6.7.1. MLCT Transitions for Triangular Pt3(CO)3(P(?-Bu)3)3 87
6.7.2. Metal-Centered Transitions in the Hg3(dppm)3+ Cluster
Complex 89
6.7.3. Pt — Au Framework and Intraframework Transitions
in the Gold Cluster Complexes Pt(AuPPh3)|+ and
Au(AuPPh3)i+ 93
CONTENTS vii
6.8. Triiodide Ion: An Example of a Pseudo A Term 97
6.9. Methyl Iodide: ? - s* and Iodine-Based 5p Rydberg
Transitions 99
6.9.1. ? —*¦ s* Transitions 100
6.9.2. Rydberg Transitions for CH3I and CD3I in the Vacuum
UV 100
6.10. Benzene: it - · ir* and Rydberg Transitions 103
6.10.1. -p -* ir* Transitions 103
6.10.2. Rydberg Transitions 108
6.11. D4/! Cyclobutadiene Dianion LI2[C4(Me3Si)4] 109
6.12. Zinc Phthalocyanine (Tetraazotetrabenzoporphyrin) Complex,
ZnPc(2-) 111
6.12.1. Vitreous Solution Spectra at Low Temperature 112
6.12.2. Matrix-Isolated ZnPc(2-) 113
6.13. Chlorophyll Q Band, An Example Using ? Terms 116
6.14. Surface Plasmon Band for Colloidal Gold Nanoparticles 119
7. Case Studies II. Paramagnetic Systems: C Terms 121
7.1. Paramagnetic Cyano Complexes 121
7.1.1. LMCT Transitions for Fe(CN)i~ 121
7.1.2. LMCT Spectra for M(CN)I~, M = Mo(V)
and W(V) 125
7.2. Ground-State Magnetization for Unstable Metallocenes 127
7.3. Determination of the Ground State for
Matrix-Isolated Manganese(II) Phthalocyanine from C Terms 129
7.4. Mononegative Cyclooctatetraene Ion (COT~) Matrix
Isolated in Argon 131
7.5. Ground-State Electronic and Structural
Information from Variable Temperature and Field Studies
of C Terms: Application to Non-Heme-Iron Enzymes 135
7.6. Modeling the Structure of the
Native Intermediate of the Multicopper Oxidase
from Rhus Vernicifera Lacease Isolated from the Japanese
Lacquer Tree 138
7.7. High-Spin Metal Centers with Ground-State
Spin 1/2; Application to the Protein-Oxidized
Rubredoxin, Desulfovibrio gigas 142
7.8. MCD of Co2+ as a Probe of Metal-Binding Sites in
E. coli Methionyl Aminopeptidase 146
7.9. Optically Detected Electron Paramagnetic
Resonance (ODEPR) by Microwave-Modulated
MCD: Application to the Optical Anisotropy of the
Blue Copper Protein Pseudomonas aeruginosa Azurin 150
viii CONTENTS
7.10. Single-Molecule Magnets (SMMs) 155
7.10.1. Spin Polarization in the S = 10 Mixed Valence
Mn(IV)-Mn(III) Cluster Complex
[Mn12O12(O2CR)16(H2O)4] 155
7.10.2. Single Ion and Cluster Spin in the
5 = 6 [Cr12O9(O2CCMe3)15] Cluster Complex 158
7.11. Lanthanide Ions in Crystalline Environments 162
7.11.1. Na3Ln(ODA)3 · 2NaC104 · 6H2O (LnODA,
Ln = Eu and Nd) 163
7.11.2. LiErF4, LiYF4/Eu3+, and KY3F1O/Eu3+Crystals 165
8. Magnetic Vibrational Circular Dichroism (MVCD) and X-Ray
Magnetic Circular Dichroism (XMCD) 171
8.1. MVCD 171
Instrumentation 172
Examples 173
MVCD for Metal Carbonyl Complexes M(CO)6,
M = Cr, Mo, and W 173
Rotationally Resolved MVCD for Carbon Monoxide 174
Rotationally Resolved MVCD for Methane 176
Rotationally Resolved MVCD for Acetylene and
Deuterated Isotopomers 176
8.2. XMCD 179
8.2.1. XMCD Measurements 179
8.2.2. Sum Rules 180
8.2.3. Magnetic Properties of GdNi2 Laves Phase 180
8.2.4. XMCD Study of Re 5d Magnetism in the Sr2CrReO6
Double Perovskite 181
8.2.5. XMCD Study of Mn(III) and Mn(IV) Magnetic
Contributions to the SMM [Mn12O)2(CH3CO2)16(H2O)24] ·
2CH3COOH · 4H2O 184
8.2.6. XMCD for Pseudomonas aeruginosa Nickel(II) Azurin
(NiAz) 187
9. Magnetic Linear Dichroism Spectroscopy 188
9.1. Introduction 188
9.2. MLD Terms and Term Parameters 188
9.3. Measurement of MLD Spectra 192
9.4. Some Examples of MLD Spectra 192
9.4.1. Atomic Mercury Vapor 193
9.4.2. Metal Atoms Isolated in Noble Gas Matrices 195
9.4.3. Lanthanide Metal Ions in Solution: Ho3+ 197
9.4.4. Ferrocytochrome c and Deoxymyoglobin 199
8. L.I.
8. 1.2.
8. L.3.
8. 1.4.
8. 1.5.
8. L.6.
CONTENTS
ix
APPENDIXES
Appendix A. Tables for the Symmetry Groups O and Td
202
Table A. 1. Function ø and Operator Op Transformation Coefficients for
Groups O and Td 202
Table A.2. 3/', 2j, and 2jm Phases in the O and Td Bases for Single-Valued
Irreps 203
Table A.3. 3jm for O and Td Bases for Single-Valued Irreps 204
Table A.4. 6/ for O and Td Bases for Single-Valued Irreps 205
Appendix B. Tables for the Fourfold Symmetry Group D4 207
Table B.I. Function ø and Operator Op Transformation Coefficients for
Group D4 207
Table B.2. 3/', 2j, and 2jm Phases in D4 Bases for Single-Valued
Irreps 207
Table B.3. 3jm in D4 Bases for Single-Valued Irreps 208
Table B.4. 6/ in D4 Bases for Single-Valued Irreps 208
Appendix C. Tables for the Threefold Symmetry Group D3 209
Table C. 1. Function ø and Operator Op Transformation Coefficients for
Group £ 3 209
Table C.2. 3/, 2j, and 2jm Phases in D3 Bases for Single-Valued
Irreps 209
Table C.3. 3jm in D3 Bases for Single-Valued Irreps 210
Table C.4. 6/ in D3 Bases for Single-Valued Irreps 210
Table D.I. Partial List of SO3 D O 3jm Factors
Appendix D. 3jm Factors for Single-Valued Irreps of the
SO3 D O and O D D4 Chains 211
\at f\ bij O
Involving Single-Valued Irreps 211
Table D.2. Partial List of O D D4 3jm Factors ( °l {' , ' ) f*
\a2 fi b2JD4
Involving Single-Valued Irreps 212
Reviews and References 213
Index
218 |
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| id | DE-604.BV022550349 |
| illustrated | Illustrated |
| index_date | 2024-07-02T18:13:18Z |
| indexdate | 2024-07-09T21:00:03Z |
| institution | BVB |
| isbn | 9780470069783 |
| language | English |
| oai_aleph_id | oai:aleph.bib-bvb.de:BVB01-015756676 |
| oclc_num | 237893171 |
| open_access_boolean | |
| owner | DE-703 DE-91G DE-BY-TUM DE-19 DE-BY-UBM |
| owner_facet | DE-703 DE-91G DE-BY-TUM DE-19 DE-BY-UBM |
| physical | XII, 223 S. graph. Darst. |
| publishDate | 2007 |
| publishDateSearch | 2007 |
| publishDateSort | 2007 |
| publisher | Wiley-Interscience |
| record_format | marc |
| spelling | Mason, W. Roy Verfasser aut A practical guide to magnetic circular dichroism spectroscopy W. Roy Mason Hoboken, NJ Wiley-Interscience 2007 XII, 223 S. graph. Darst. txt rdacontent n rdamedia nc rdacarrier Dichroïsme circulaire magnétique Molécules - Spectre Spectroscopie moléculaire Faraday-Effekt (DE-588)4153684-8 gnd rswk-swf CD-Spektroskopie (DE-588)4714754-4 gnd rswk-swf CD-Spektroskopie (DE-588)4714754-4 s Faraday-Effekt (DE-588)4153684-8 s DE-604 HBZ Datenaustausch application/pdf http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=015756676&sequence=000002&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA Inhaltsverzeichnis |
| spellingShingle | Mason, W. Roy A practical guide to magnetic circular dichroism spectroscopy Dichroïsme circulaire magnétique Molécules - Spectre Spectroscopie moléculaire Faraday-Effekt (DE-588)4153684-8 gnd CD-Spektroskopie (DE-588)4714754-4 gnd |
| subject_GND | (DE-588)4153684-8 (DE-588)4714754-4 |
| title | A practical guide to magnetic circular dichroism spectroscopy |
| title_auth | A practical guide to magnetic circular dichroism spectroscopy |
| title_exact_search | A practical guide to magnetic circular dichroism spectroscopy |
| title_exact_search_txtP | A practical guide to magnetic circular dichroism spectroscopy |
| title_full | A practical guide to magnetic circular dichroism spectroscopy W. Roy Mason |
| title_fullStr | A practical guide to magnetic circular dichroism spectroscopy W. Roy Mason |
| title_full_unstemmed | A practical guide to magnetic circular dichroism spectroscopy W. Roy Mason |
| title_short | A practical guide to magnetic circular dichroism spectroscopy |
| title_sort | a practical guide to magnetic circular dichroism spectroscopy |
| topic | Dichroïsme circulaire magnétique Molécules - Spectre Spectroscopie moléculaire Faraday-Effekt (DE-588)4153684-8 gnd CD-Spektroskopie (DE-588)4714754-4 gnd |
| topic_facet | Dichroïsme circulaire magnétique Molécules - Spectre Spectroscopie moléculaire Faraday-Effekt CD-Spektroskopie |
| url | http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=015756676&sequence=000002&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA |
| work_keys_str_mv | AT masonwroy apracticalguidetomagneticcirculardichroismspectroscopy |