{"title":"高磁场下耦合核自旋系综的磁化和极化。","authors":"Danila A Barskiy, Andrey N Pravdivtsev","doi":"10.1002/cphc.202500092","DOIUrl":null,"url":null,"abstract":"<p><p>In nuclear magnetic resonance (NMR), the bulk magnetization of a sample is commonly assumed to be proportional to spin polarization, with each spin of the same type contributing equally to the measured signal. Herein, the high-field theorem for general spin-I systems (where I is the spin quantum number): the total measurable NMR signal remains unaffected by the grouping of spins into equivalent units (e.g., molecules) is proved, provided the system is at thermodynamic equilibrium in the high field limit ( <math> <semantics><mrow><mi>ℏ</mi> <msub><mi>ω</mi> <mn>0</mn></msub> <mo>≫</mo> <mo>|</mo> <msub><mi>H</mi> <mrow><mtext>spin</mtext> <mo>-</mo> <mtext>spin</mtext></mrow> </msub> <mo>|</mo></mrow> <annotation>$$ \\hslash {\\omega }_{0}\\gg |{H}_{\\text{spin}-\\text{spin}}|$$</annotation></semantics> </math> , where <math> <semantics> <mrow><msub><mi>ω</mi> <mn>0</mn></msub> </mrow> <annotation>$\\left(\\omega\\right)_{0}$</annotation></semantics> </math> is the Larmor frequency and <math> <semantics> <mrow><mrow><mo>|</mo> <mrow><msub><mi>H</mi> <mrow><mtext>spin</mtext> <mo>-</mo> <mtext>spin</mtext></mrow> </msub> </mrow> <mo>|</mo></mrow> </mrow> <annotation>$\\left|\\right. H_{\\text{spin} - \\text{spin}} \\left|\\right.$</annotation></semantics> </math> characterizes internal spin-spin interactions). The results are derived using both magnetization equations and density matrix formalism. The theorem, however, does not extend to conditions far from thermodynamic equilibrium (e.g., hyperpolarization), NMR of solids in the regime when quadrupolar or dipole-dipole interactions are not negligible, and zero- to ultralow-field NMR. Three educational problems designed to deepen understanding of the material in classroom settings are also presented. This work reinforces established principles in magnetic resonance but also highlights areas for further exploration.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e2500092"},"PeriodicalIF":2.3000,"publicationDate":"2025-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Magnetization and Polarization of Coupled Nuclear Spins Ensembles at High Magnetic Fields.\",\"authors\":\"Danila A Barskiy, Andrey N Pravdivtsev\",\"doi\":\"10.1002/cphc.202500092\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p><p>In nuclear magnetic resonance (NMR), the bulk magnetization of a sample is commonly assumed to be proportional to spin polarization, with each spin of the same type contributing equally to the measured signal. Herein, the high-field theorem for general spin-I systems (where I is the spin quantum number): the total measurable NMR signal remains unaffected by the grouping of spins into equivalent units (e.g., molecules) is proved, provided the system is at thermodynamic equilibrium in the high field limit ( <math> <semantics><mrow><mi>ℏ</mi> <msub><mi>ω</mi> <mn>0</mn></msub> <mo>≫</mo> <mo>|</mo> <msub><mi>H</mi> <mrow><mtext>spin</mtext> <mo>-</mo> <mtext>spin</mtext></mrow> </msub> <mo>|</mo></mrow> <annotation>$$ \\\\hslash {\\\\omega }_{0}\\\\gg |{H}_{\\\\text{spin}-\\\\text{spin}}|$$</annotation></semantics> </math> , where <math> <semantics> <mrow><msub><mi>ω</mi> <mn>0</mn></msub> </mrow> <annotation>$\\\\left(\\\\omega\\\\right)_{0}$</annotation></semantics> </math> is the Larmor frequency and <math> <semantics> <mrow><mrow><mo>|</mo> <mrow><msub><mi>H</mi> <mrow><mtext>spin</mtext> <mo>-</mo> <mtext>spin</mtext></mrow> </msub> </mrow> <mo>|</mo></mrow> </mrow> <annotation>$\\\\left|\\\\right. H_{\\\\text{spin} - \\\\text{spin}} \\\\left|\\\\right.$</annotation></semantics> </math> characterizes internal spin-spin interactions). The results are derived using both magnetization equations and density matrix formalism. The theorem, however, does not extend to conditions far from thermodynamic equilibrium (e.g., hyperpolarization), NMR of solids in the regime when quadrupolar or dipole-dipole interactions are not negligible, and zero- to ultralow-field NMR. Three educational problems designed to deepen understanding of the material in classroom settings are also presented. This work reinforces established principles in magnetic resonance but also highlights areas for further exploration.</p>\",\"PeriodicalId\":9819,\"journal\":{\"name\":\"Chemphyschem\",\"volume\":\" \",\"pages\":\"e2500092\"},\"PeriodicalIF\":2.3000,\"publicationDate\":\"2025-04-23\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Chemphyschem\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1002/cphc.202500092\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q3\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Chemphyschem","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1002/cphc.202500092","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
Magnetization and Polarization of Coupled Nuclear Spins Ensembles at High Magnetic Fields.
In nuclear magnetic resonance (NMR), the bulk magnetization of a sample is commonly assumed to be proportional to spin polarization, with each spin of the same type contributing equally to the measured signal. Herein, the high-field theorem for general spin-I systems (where I is the spin quantum number): the total measurable NMR signal remains unaffected by the grouping of spins into equivalent units (e.g., molecules) is proved, provided the system is at thermodynamic equilibrium in the high field limit ( , where is the Larmor frequency and characterizes internal spin-spin interactions). The results are derived using both magnetization equations and density matrix formalism. The theorem, however, does not extend to conditions far from thermodynamic equilibrium (e.g., hyperpolarization), NMR of solids in the regime when quadrupolar or dipole-dipole interactions are not negligible, and zero- to ultralow-field NMR. Three educational problems designed to deepen understanding of the material in classroom settings are also presented. This work reinforces established principles in magnetic resonance but also highlights areas for further exploration.
期刊介绍:
ChemPhysChem is one of the leading chemistry/physics interdisciplinary journals (ISI Impact Factor 2018: 3.077) for physical chemistry and chemical physics. It is published on behalf of Chemistry Europe, an association of 16 European chemical societies.
ChemPhysChem is an international source for important primary and critical secondary information across the whole field of physical chemistry and chemical physics. It integrates this wide and flourishing field ranging from Solid State and Soft-Matter Research, Electro- and Photochemistry, Femtochemistry and Nanotechnology, Complex Systems, Single-Molecule Research, Clusters and Colloids, Catalysis and Surface Science, Biophysics and Physical Biochemistry, Atmospheric and Environmental Chemistry, and many more topics. ChemPhysChem is peer-reviewed.