Posted by **Edward d'Auvergne** on January 08, 2009 - 11:19:

Hi, Warning: If hard core NMR or physics theory is not to your taste, please do not read any further! This post is mainly for later reference, but is quite important for understanding the relaxation equations in NMR, and actually any rotational physical process. It is important for the model-free equations, for reduced spectral density mapping, for SRLS, and for relaxation dispersion. The reason is because R1 and R2 are measured in rad/s. As I describe in section 1, the radian unit can be dropped because it is plainly obvious that NMR and relaxation is an angular process and hence radian units are implied (that was sarcastic). Hence R2 can be said to be in units of 1/s, but never, ever Hz. Also note that because of the SI conventions described below, describing the correlation time in s units does not prove that there are no radian units. But reporting rates as Hz implies no radian units whereas reporting as 1/s instead often means radian units are present. This is also a follow on from the comprehensive unit analysis of Abragam's relaxation equations at https://mail.gna.org/public/relax-devel/2007-06/msg00012.html. Keywords (for finding this post at a later date): diffusion rates, dimensionless units, hidden units, radian, relaxation rates, rotational correlation times, SI supplementary units, spherical harmonics. 1 SI supplementary units. 1.1 SI supplementary units (radian and steradian). Quote from the PDF linked below (page 26) in the table titled "Table 3. Coherent derived units in the SI with special names and symbols" about the 'SI coherent derived unit' for the 'plane angle' unit of radian: "(b) The radian and steradian are special names for the number one that may be used to convey information about the quantity concerned. In practice the symbols rad and sr are used where appropriate, but the symbol for the derived unit one is generally omitted in specifying the values of dimensionless quantities." Quote from the PDF linked below (page 28) in the section titled "2.2.3 Units for dimensionless quantities, also called quantities of dimension one": "In a few cases, however, a special name is given to the unit one, in order to facilitate the identification of the quantity involved. This is the case for the radian and the steradian. The radian and steradian have been identified by the CGPM as special names for the coherent derived unit one, to be used to express values of plane angle and solid angle, respectively, and are therefore included in Table 3." Quote from the PDF linked below (page 42) in the section titled "5.3.7 Stating values of dimensionless quantities, or quantities of dimension one". This is not very clear but explains why the rad unit is many times hidden, and why the other dimensionless units such as % and ppm must be stated (need to read the whole section for that): "As discussed in Section 2.2.3, the coherent SI unit for dimensionless quantities, also termed quantities of dimension one, is the number one, symbol 1. Values of such quantities are expressed simply as numbers. The unit symbol 1 or unit name "one" are not explicitly shown, nor are special symbols or names given to the unit one, apart from a few exceptions as follows. For the quantity plane angle, the unit one is given the special name radian, symbol rad, and for the quantity solid angle, the unit one is given the special name steradian, symbol sr. For the logarithmic ratio quantities, the special names neper, symbol Np, bel, symbol B, and decibel, symbol dB, are used (see 4.1 and Table 8, p. 127)." Quotes from the PDF linked below (page 67) from the appendix section titled "SI supplementary units (radian and steradian)": "...the units radian and steradian are usually introduced into expressions for units when there is need for clarification..." Quote from the PDF linked below (page 67) from the appendix section titled "Elimination of the class of supplementary units in the SI" for resolution 8 of the CGPM conference: "decides..." "to interpret the supplementary units in the SI, namely the radian and the steradian, as dimensionless derived units, the names and symbols of which may, but need not, be used in expressions for other SI derived units, as is convenient," "and, consequently, to eliminate the class of supplementary units as a separate class in the SI." Links: http://www.bipm.org/en/si/si_brochure/ http://www.bipm.org/utils/common/pdf/si_brochure_8_en.pdf 1.2 IUPAC report. This reference explains a bit more clearly why the radian unit is invisible in most situations. Title: Quantities, units, and symbols in physical chemistry (second edition). Quote from page 11: "The units radian (rad) and steradian (sr), for plane angle and solid angle respectively, are described as 'SI supplementary units' [3]. Since they are of dimension 1 (i.e. dimensionless), they may be included if appropriate, or they may be omitted if clarity is not lost thereby, in expressions for derived SI units." This is the part meaning that radians are implied if you are doing anything angular. I don't know what they mean by clarity because by omitting them it complicates things. Maybe you have to be a physicist before you can see this clarity. 2 Spherical harmonics. The time dependent spherical harmonic can be written as Y_ml(theta(t), phi(t)), where theta(t) and phi(t) are the time dependent spherical angles in the dimensionless radian units. The time t is normal time and hence has no hidden radian units. Spherical harmonics are the angular portion of the solution to Laplace's equation, and I would assume that because it is angular, it is using the radian angular SI unit. 3 Rotational correlation times. My opinion here is that the rotational correlation time is a descriptor of the change of angles - and these angles are in the hidden, dimensionless radian units. Hence the correlation time is measured in s/rad or in the hidden supplementary unit notation simply s. But I prefer to think of the concept as the diffusion rate, a measure of the rate of rotational Brownian diffusion. 3.1 Book quotations. Title: Physical Properties of Lipids Authors: Alejandro G. Marangoni, Suresh Narine Subject: Fluorescence Year: 2002 Link: http://books.google.com/books?id=OCBav13l_MsC&pg=PA166&dq=rotational+correlation+time+radian&lr= Quote (page 166): "The rotational correlation time [phi] is the time required by the fluorophore to rotate through an arc of 1 radian (phi = 1/(2.pi.nu))." Title: Biophysics Authors: Gerald Ehrenstein, Harold Lecar Subject: NMR spin relaxation Year: 1982 Link: http://books.google.com/books?id=rThFVFmAdDAC&pg=PA14&dq=rotational+correlation+time+radian Quote (page 14): "The value of tau_c can be approximated as the time required for the molecule containing the resonant nucleus to either rotate 1 radian (rotational correlation time) or diffuse a distance equivalent to its own dimensions (translational correlation time)." Title: Protein NMR Spectroscopy (second edition) Authors: John Cavanagh, Wayne J. Fairbrother, Arthur G. Palmer, III, Nicholas J. Skelton, Mark Rance Subject: NMR relaxation Year: 2007 Link: http://books.google.com/books?id=2-LqLHOLHZwC&pg=PA366&dq=rotational+correlation+time+radian Quote (page 366): "...in which the correlation time, tau_c, is approximately the average time for the molecule to rotate by 1 radian." Title: Hydration Processes in Biology: Theoretical and Experimental Approaches Author: Marie-Claire Bellissent-Funel Subject: Water motion Year: 1999 Link: http://books.google.com/books?id=9tJaB00wXhgC&pg=PA243&dq=rotational+correlation+time+radian&lr= Quote (page 243): "For such sites, the rotational and translational diffusion of water should both be rate-limited by H-bond rearrangements and it can therefore be argued that the residence time (the time taken to diffusion ca. 3 Angstrom) should be close to the first-rank rotational correlation time (the time taken to rotate through one radian), i.e., tau_W ~= 3 tau_s (where tau_s is the second-rank rotational correlation time)." (Interesting that the factor of 3 is only approximate here!!! Nils, do you have a citation where the equation is not appriximate?) Title: NMR of Macromolecules: A Practical Approach Author: Gordon Carl Kenmure Roberts Subject: NMR relaxation Year: 1993 Link: http://books.google.com/books?id=K7n7SnmDbSAC&pg=PA9&dq=rotational+correlation+time+radian&lr= Quote (page 9): "The rotational correlation time, tau_c, is the time taken for the particle to rotate through an angle of one radian (57°)." Title: Fundamentals of Protein NMR Spectrosopy Authors: Gordon S. Rule, T. Kevin Hitchens Subject: NMR relaxation Year: 2006 Link: http://books.google.com/books?id=8vmf5y6Jf84C&pg=PA441&dq=rotational+correlation+time+radian Quote (page 441): "[tau_c] is the time required for a molecule to rotate, on average, 1 radian." Title: Nuclear Magnetic Resonance in Biochemistry: Principles and Applications Author: Thomas L. James Subject: NMR Year: 1975 Link: http://books.google.com/books?id=iItqAAAAMAAJ&q=rotational+correlation+time+radian&dq=rotational+correlation+time+radian&pgis=1 Quote (page ?): "The rotational correlation time (rc or rr) provides a ... having many molecular collisions before it turns 1 radian." Title: Biophysical Chemistry: Principles, Techniques, and Applications Author: Alan G. Marshall Subject: Rotational diffusion (for fluorescence) Year: 1978 Link: http://books.google.com/books?id=PJhqAAAAMAAJ&q=rotational+correlation+time+radian&dq=rotational+correlation+time+radian&pgis=1 Quote (page 720): "...decay of the correlation function for rotational diffusion, tau_rot may also be thought of as the characteristic time it takes for a typical macromolecule to rotate (diffusionally) through an angle of the order of a radian..." Title: Practical NMR Relaxation for Chemists Author: Vladimir I. Bakhmutov Subject: NMR relaxation Year: 2004 Link: http://books.google.com/books?id=_gIh9KHIOx4C&pg=PA13&dq=rotational+correlation+time+radian&lr= Quote (page 13): "However, a more correct definition of the tau_c is connected with the, so-called autocorrelation function in the theory of nuclear relaxation where the tau_c is an average time for the molecule to progresses (sic.) through one radian." Title: Modern Protein Chemistry: Practical Aspects Authors: Gary C. Howard, William E. Brown Subject: NMR relaxation Year: 2001 Link: http://books.google.com/books?id=MIxdC7GPz0sC&pg=PA45&dq=rotational+correlation+time+radian&lr= Quote (page 45): "[tau_c] is roughly equal to the time it takes a molecule to rotate 1 radian while undergoing random rotational motion." Title: MRS of the Brain and Neurological Disorders Authors: Koji Terada, Akihiro Igata, Toshiro Fujimoto, Tetsuhiko Asakura, Institute of Advanced Medical Technology Subject: Imaging Year: 2000 Link: http://books.google.com/books?id=kF2dw7c33cAC&pg=PA41&dq=rotational+correlation+time+radian&lr=#PPA43,M1 Quote (page 41): "...Brownian motion. This has a time scale, the rotational correlation time (tau_c) defined as the time taken on average for a solute molecule to rotate by one radian or roughly the reciprocal of the rate of tumbling in solution of the relevant piece of the molecule." Title: Structural Biology: Practical NMR Applications Author: Quincy Teng Subject: NMR relaxation Year: 2005 Link: http://books.google.com/books?id=dRmmGFkummIC&pg=PA36&dq=rotational+correlation+time+radian&lr=#PPA36,M1 Quote (page 36): "The correlation time is used to describe the rate of random motions and is expressed as the average time between collisions for translational motions or the time for a molecule to rotate one radian in rotational motion." Title: High-resolution NMR Techniques in Organic Chemistry Author: Timothy D. W. Claridge Subject: NMR relaxation Year: 1999 Link: http://books.google.com/books?id=9srIkkL-YMkC&pg=PA283&dq=rotational+correlation+time+radian&lr=#PPA284,M1 Quote (page 283): "... its rotational correlation time, tau_c. This is usually taken to define the average time required for the molecule to rotate through an angle of 1 radian about any axis, ..." Title: A Dictionary of Concepts in NMR Author: S. W. Homans Subject: NMR relaxation Year: 1989 Link: http://books.google.com/books?id=wpggNxUrzSMC&pg=PA72&dq=rotational+correlation+time+radian&lr= Quote (page 72): "For example, in the case of random translational motions, tau_c is defined as the mean time between collisions, whereas in the case of reorientational (rotational) motion, it is defined as the average time for the molecule to rotate by one radian." Note this book later on page 72 makes the mistake (according to me) of saying that 1/tau_c is in Hertz. Title: Molecular Crystals and Liquid Crystals Author: Gordon and Breach Science Publishers Subject: Crystals Year: 1974 Link: http://books.google.com/books?id=bTW3AAAAIAAJ&q=rotational+correlation+time+radian&dq=rotational+correlation+time+radian&lr=&pgis=1 Quote (page ?): "The rotational correlation time may be computed from the linewidths of the ... roughly the time required for the radical to reorient by 1 radian is given by ..." Title: Industrial Research/development Author: Technical Pub. Co. Subject: NMR relaxation Year: 1978 Link: http://books.google.com/books?id=EstVAAAAMAAJ&q=rotational+correlation+time+radian&dq=rotational+correlation+time+radian&lr=&pgis=1 Quote (page ?): " is the Larmor angular frequency in radians/sec and tau_c is the rotational correlation time of the nuclei in sec/radian." 4 Relaxation rates Here, my opinion is that the R1 and R2 units are rad/s. The equations from the book quotations hopefully show this conversion from Hz to rad/s. 4.1 Book quotations. Title: Nuclear Spin Relaxation in Liquids: Theory, Experiments, and Applications Authors: Józef Kowalewski, Lena Mäler Subject: NMR relaxation Year: 2006 Link: http://books.google.com/books?id=MiUfcE1C9CQC&pg=PA14&dq=relaxation+rate+radian&lr=#PPA19,M1 Quote (page 15): "Because the natural unit for the angular frequency is radians per second, the relaxation rate, or the inverse of relaxation time, R2 = 1/T2, should indeed also be expressed in these units. Usually, relaxation times are given in seconds (the rates are given in 1/s), which tacitly implies that the radians can be omitted; we note in parenthesis that the radian is considered a dimensionless unit in physics." Quote 2 (page 15): "The Fourier transform of an exponential decay is Lorentzian centered at zero frequency, with the full width at half-height (in Hertz) equal to Delta_nu = 1/(pi.T2)..." Title: Practical NMR Relaxation for Chemists Author: Vladimir I. Bakhmutov Subject: NMR relaxation Year: 2004 Link: http://books.google.com/books?id=_gIh9KHIOx4C&pg=PA13&dq=rotational+correlation+time+radian&lr= Quote (page 9): "...linewidths, Delta_nu, measured in Hz, are directly controlled by T1 and T2 relaxation times according to: Delta_nu = 1/(pi T1,2)" Title: Modern Protein Chemistry: Practical Aspects Authors: Gary C. Howard, William E. Brown Subject: NMR relaxation Year: 2001 Link: http://books.google.com/books?id=MIxdC7GPz0sC&pg=PA45&dq=rotational+correlation+time+radian&lr= Quote (page 45): "The actual relationship between the spin-spin relation rate and the lines width (Delta_nu) is given by R2, the rate of spin-spin relaxation; T2 is the time constant for spin-spin relaxation, Delta_nu = 1/pi . R2 = 1/(pi.T2)." Title: Structural Biology: Practical NMR Applications Author: Quincy Teng Subject: NMR relaxation Year: 2005 Link: http://books.google.com/books?id=dRmmGFkummIC&pg=PA36&dq=rotational+correlation+time+radian&lr=#PPA36,M1 Quote (page 37): "...T1 relaxation is inversely proportional to correlation time tau_c..." Apologies for the length, but this is designed to be a comprehensive reference for future use. Regards, Edward

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