general

Differences

This shows you the differences between two versions of the page.

Link to this comparison view

Both sides previous revision Previous revision
Next revision		 Previous revision
Next revisionBoth sides next revision
general [2019/10/04 17:13] – [Special Considerations for 'l'-doubled States] admingeneral [2019/10/04 17:23] – change some headers admin
Line 87: Line 87:
 The freeform input begins in column 37 and extends to the end of the line. The freeform input begins in column 37 and extends to the end of the line.
 See the notes at the end of the next section for more on the freeform input. See the notes at the end of the next section for more on the freeform input.
 +
 ===== Format of the ''par'' and ''var'' Files ===== ===== Format of the ''par'' and ''var'' Files =====
  
Line 149: Line 150:
 **NOTE:** For many cases only a single option line is needed. If different vibronic states have different spin multiplicity or different KMIN, KMAX additional lines are needed. Note that additional lines are signaled by the sign of VSYM. The first option line sets up the defaults for all the vibrational states, and subsequent option lines specify deviations from the default. It is possible to mix Boson and Fermion states in the same calculation, e.g. fitting different isotopomers together, but the quantum number format (QNFMT) in SPCAT output will be correct only for the v = 0 state. **NOTE:** For many cases only a single option line is needed. If different vibronic states have different spin multiplicity or different KMIN, KMAX additional lines are needed. Note that additional lines are signaled by the sign of VSYM. The first option line sets up the defaults for all the vibrational states, and subsequent option lines specify deviations from the default. It is possible to mix Boson and Fermion states in the same calculation, e.g. fitting different isotopomers together, but the quantum number format (QNFMT) in SPCAT output will be correct only for the v = 0 state.
 </alert> </alert>
 +
 +===== Coding of the Parameters =====
 +
 ==== Parameter lines: IDPAR, PAR, ERRPAR / LABEL ==== ==== Parameter lines: IDPAR, PAR, ERRPAR / LABEL ====
  
Line 219: Line 223:
 If IDPAR is less than zero the magnitude is taken. In SPFIT, the parameter value will be constrained to be a constant ratio of the preceding parameter value. In this way linear combinations of parameters can be fit as a unit. If IDPAR is less than zero the magnitude is taken. In SPFIT, the parameter value will be constrained to be a constant ratio of the preceding parameter value. In this way linear combinations of parameters can be fit as a unit.
  
-===== Coding of the Parameters ===== +==== Format of the ''int'' File ====
- +
-===== Format of the ''int'' File =====+
  
 **line 1:** title **line 1:** title
Line 294: Line 296:
 **NOTE:** Dipoles with SYM > 0 are assumed to be in units of Debye. Dipoles with SYM = 0 are assumed to be in units of a Bohr magneton. Dipoles which are even order in direction cosine or N are assumed to be imaginary, except between states with EWT1 = 1. Dipoles between states with EWT1 = (0,2), (2,0), and (2,2) are ignored, but the matrix elements are calculated using corresponding dipoles from states with EWT1 = 1 (see below). For ITYP = 7 or ITYP = 8, I1 is used for the Fourier order and not the spin type. The constant r is specified in the parameter set. The sign of the r parameter is used to designate a special symmetry for the Fourier series.  If this sign is different for V1 and V2, then 0.5 is subtracted from the Fourier order.  For example, if IDIP = 72012, the basic //b//-dipole operator is multiplied by cos ( 3p K<sub>avg</sub>r / 3) instead of cos (4p K<sub>avg</sub>r / 3).  If the magnitude of  r is not the same for the two states, replace K<sub>avg</sub>r with (K<sub>1</sub>r<sub>1</sub> + K<sub>2</sub>r<sub>2</sub>) / 2. ITYP = 8 (with I1 > 0) dipoles are multiplied by //i//, and the symmetry of the states connected is 3 – SYM and the units follow the state symmetry (e.g. 81000 is in Debye ). ITYP = 2, 5 are used for first-order Herman-Wallis corrections. ITYP = 3, 4, 6, 11, 12 are used for second-order Herman-Wallis corrections. **NOTE:** Dipoles with SYM > 0 are assumed to be in units of Debye. Dipoles with SYM = 0 are assumed to be in units of a Bohr magneton. Dipoles which are even order in direction cosine or N are assumed to be imaginary, except between states with EWT1 = 1. Dipoles between states with EWT1 = (0,2), (2,0), and (2,2) are ignored, but the matrix elements are calculated using corresponding dipoles from states with EWT1 = 1 (see below). For ITYP = 7 or ITYP = 8, I1 is used for the Fourier order and not the spin type. The constant r is specified in the parameter set. The sign of the r parameter is used to designate a special symmetry for the Fourier series.  If this sign is different for V1 and V2, then 0.5 is subtracted from the Fourier order.  For example, if IDIP = 72012, the basic //b//-dipole operator is multiplied by cos ( 3p K<sub>avg</sub>r / 3) instead of cos (4p K<sub>avg</sub>r / 3).  If the magnitude of  r is not the same for the two states, replace K<sub>avg</sub>r with (K<sub>1</sub>r<sub>1</sub> + K<sub>2</sub>r<sub>2</sub>) / 2. ITYP = 8 (with I1 > 0) dipoles are multiplied by //i//, and the symmetry of the states connected is 3 – SYM and the units follow the state symmetry (e.g. 81000 is in Debye ). ITYP = 2, 5 are used for first-order Herman-Wallis corrections. ITYP = 3, 4, 6, 11, 12 are used for second-order Herman-Wallis corrections.
 </alert> </alert>
-===== Format of the ''cat'' File =====+==== Format of the ''cat'' File ====
  
 **[F13.4, 2F8.4, I2, F10.4, I3, I7, I4, 12I2]:** FREQ, ERR, LGINT, DR, ELO, GUP, TAG, QNFMT, QN **[F13.4, 2F8.4, I2, F10.4, I3, I7, I4, 12I2]:** FREQ, ERR, LGINT, DR, ELO, GUP, TAG, QNFMT, QN
Line 308: Line 310:
 > QN(12) = Quantum numbers coded according to QNFMT. Upper state quanta start in character 1. Lower state quanta start in character 14. Unused quanta are blank, quanta whose magnitude is larger than 99 or smaller than –9 are shown with alphabetic characters or %%**%%. Quanta between –10 and –19 are shown as a0 through a9. Similarly, –20 is b0, etc., up to –259, which is shown as z9. Quanta between 100 and 109 are shown as A0 through A9. Similarly, 110 is B0, etc., up to 359, which is shown as Z9. > QN(12) = Quantum numbers coded according to QNFMT. Upper state quanta start in character 1. Lower state quanta start in character 14. Unused quanta are blank, quanta whose magnitude is larger than 99 or smaller than –9 are shown with alphabetic characters or %%**%%. Quanta between –10 and –19 are shown as a0 through a9. Similarly, –20 is b0, etc., up to –259, which is shown as z9. Quanta between 100 and 109 are shown as A0 through A9. Similarly, 110 is B0, etc., up to 359, which is shown as Z9.
  
-===== Format of the ''str'' File =====+==== Format of the ''str'' File ====
  
 **[F15.4, E15.6, I5, 1X, 24A, I5]:** FREQ, DIPOLE, QNFMT, QN, ITEM **[F15.4, E15.6, I5, 1X, 24A, I5]:** FREQ, DIPOLE, QNFMT, QN, ITEM
Line 318: Line 320:
 > ITEM = identifies number of dipole > ITEM = identifies number of dipole
  
-===== Format of the ''egy'' File =====+==== Format of the ''egy'' File ====
  
 **energy output [2I5, 3F18.6, 6I3]:** IBLK, INDX, EGY, PMIX, ERR, QN **energy output [2I5, 3F18.6, 6I3]:** IBLK, INDX, EGY, PMIX, ERR, QN
Line 398: Line 400:
 The //K// quantum numbers for  //l//-doubled states are designated specially when asymmetric rotor quanta are used so that the lower //K// doublet is associated with the EWT1 = 1 state and the upper //K// doublet and //K// = 0 states are assiciated with EWT1 = 2.  In this way the degenerate states have the same quantum numbers. The //K// quantum numbers for  //l//-doubled states are designated specially when asymmetric rotor quanta are used so that the lower //K// doublet is associated with the EWT1 = 1 state and the upper //K// doublet and //K// = 0 states are assiciated with EWT1 = 2.  In this way the degenerate states have the same quantum numbers.
  
-===== Some Examples =====+=====  Simple Examples ===== 
 + 
 +Example of parameter types for asymmetric rotors (assuming < 10 vibronic states): 
 + 
 +|11       |energy for v = 1                                                     | 
 +|01       |first order Fermi (F<sub>0</sub>) interaction between v = 0 and v = 1| 
 +|10000    |A<sub>00</sub>                                                       | 
 +|10099    |A (for all vibrational states)                                       | 
 +|20099    |B (dito)                                                             | 
 +|30099    |C (dito)                                                             | 
 +|40099    |0.25*(B – C)  (if prolate basis selected)                            | 
 +|299      |–D<sub>J</sub>                                                       | 
 +|1199     |–D<sub>JK</sub>                                                      | 
 +|2000     |–D<sub>K</sub> for v = 0                                             | 
 +|600001   |i N<sub>c</sub> interaction between v = 0 and v = 1                  | 
 +|20000099 |N·I for second spin                                                  | 
 +|120010099|S<sub>a</sub> I<sub>a</sub>                                          | 
 +|220010099|1.5*c<sub>zz</sub> for second spin                                   | 
 +|220040099|0.25*(c<sub>xx</sub>–c<sub>yy</sub>) for second spin                 | 
 + 
 +Quadrupole and magnetic spin-spin interactions are defined to be traceless (i.e. c<sub>xx</sub> + c<sub>yy</sub> + c<sub>zz</sub> = 0 or T<sub>xx</sub> + T<sub>yy</sub> + T<sub>zz</sub> = 0). Therefore, all three components cannot be fit simultaneously. The most efficient choice of parameters is shown in the table below. In cases where the user wants an alternative, it is possible to use constrained parameters. For example, to fit c<sub>aa</sub> and c<sub>cc</sub> (with no multipliers): 
 + 
 +''%% 220010099   100.%%''\\ 
 +''%%–220020099  –100.%%''\\ 
 +''%% 220030099    50.%%''\\ 
 +''%%–220020099   –50.%%'' 
 + 
 +specifies c<sub>aa</sub> = 100, c<sub>cc</sub> = 50, and c<sub>bb</sub> = –150.
  
 ===== Installation Instructions ===== ===== Installation Instructions =====
  • general.txt
  • Last modified: 2023/11/07 12:40
  • by mueller