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44 #include "gromacs/legacyheaders/typedefs.h"
45 #include "gromacs/legacyheaders/macros.h"
46 #include "gromacs/legacyheaders/copyrite.h"
47 #include "gromacs/utility/futil.h"
49 #include "gromacs/legacyheaders/txtdump.h"
51 #include "gromacs/topology/mtop_util.h"
52 #include "gromacs/math/units.h"
55 #include "gromacs/commandline/pargs.h"
56 #include "gromacs/fileio/mtxio.h"
57 #include "gromacs/fileio/xvgr.h"
58 #include "gromacs/linearalgebra/eigensolver.h"
59 #include "gromacs/linearalgebra/sparsematrix.h"
60 #include "gromacs/math/vec.h"
61 #include "gromacs/utility/smalloc.h"
63 static double cv_corr(double nu, double T)
65 double x = PLANCK*nu/(BOLTZ*T);
74 return BOLTZ*KILO*(ex*sqr(x)/sqr(ex-1) - 1);
78 static double u_corr(double nu, double T)
80 double x = PLANCK*nu/(BOLTZ*T);
89 return BOLTZ*T*(0.5*x - 1 + x/(ex-1));
93 static int get_nharm_mt(gmx_moltype_t *mt)
95 static int harm_func[] = { F_BONDS };
99 for (i = 0; (i < asize(harm_func)); i++)
102 nh += mt->ilist[ft].nr/(interaction_function[ft].nratoms+1);
107 static int get_nvsite_mt(gmx_moltype_t *mt)
109 static int vs_func[] = {
110 F_VSITE2, F_VSITE3, F_VSITE3FD, F_VSITE3FAD,
111 F_VSITE3OUT, F_VSITE4FD, F_VSITE4FDN, F_VSITEN
116 for (i = 0; (i < asize(vs_func)); i++)
119 nh += mt->ilist[ft].nr/(interaction_function[ft].nratoms+1);
124 static int get_nharm(gmx_mtop_t *mtop, int *nvsites)
130 for (j = 0; (j < mtop->nmolblock); j++)
132 mt = mtop->molblock[j].type;
133 nh += mtop->molblock[j].nmol * get_nharm_mt(&(mtop->moltype[mt]));
134 nv += mtop->molblock[j].nmol * get_nvsite_mt(&(mtop->moltype[mt]));
141 nma_full_hessian(real * hess,
154 natoms = top->atoms.nr;
156 /* divide elements hess[i][j] by sqrt(mas[i])*sqrt(mas[j]) when required */
160 for (i = 0; (i < natoms); i++)
162 for (j = 0; (j < DIM); j++)
164 for (k = 0; (k < natoms); k++)
166 mass_fac = gmx_invsqrt(top->atoms.atom[i].m*top->atoms.atom[k].m);
167 for (l = 0; (l < DIM); l++)
169 hess[(i*DIM+j)*ndim+k*DIM+l] *= mass_fac;
176 /* call diagonalization routine. */
178 fprintf(stderr, "\nDiagonalizing to find vectors %d through %d...\n", begin, end);
181 eigensolver(hess, ndim, begin-1, end-1, eigenvalues, eigenvectors);
183 /* And scale the output eigenvectors */
184 if (bM && eigenvectors != NULL)
186 for (i = 0; i < (end-begin+1); i++)
188 for (j = 0; j < natoms; j++)
190 mass_fac = gmx_invsqrt(top->atoms.atom[j].m);
191 for (k = 0; (k < DIM); k++)
193 eigenvectors[i*ndim+j*DIM+k] *= mass_fac;
203 nma_sparse_hessian(gmx_sparsematrix_t * sparse_hessian,
217 natoms = top->atoms.nr;
220 /* Cannot check symmetry since we only store half matrix */
221 /* divide elements hess[i][j] by sqrt(mas[i])*sqrt(mas[j]) when required */
225 for (iatom = 0; (iatom < natoms); iatom++)
227 for (j = 0; (j < DIM); j++)
230 for (k = 0; k < sparse_hessian->ndata[row]; k++)
232 col = sparse_hessian->data[row][k].col;
234 mass_fac = gmx_invsqrt(top->atoms.atom[iatom].m*top->atoms.atom[katom].m);
235 sparse_hessian->data[row][k].value *= mass_fac;
240 fprintf(stderr, "\nDiagonalizing to find eigenvectors 1 through %d...\n", neig);
243 sparse_eigensolver(sparse_hessian, neig, eigenvalues, eigenvectors, 10000000);
245 /* Scale output eigenvectors */
246 if (bM && eigenvectors != NULL)
248 for (i = 0; i < neig; i++)
250 for (j = 0; j < natoms; j++)
252 mass_fac = gmx_invsqrt(top->atoms.atom[j].m);
253 for (k = 0; (k < DIM); k++)
255 eigenvectors[i*ndim+j*DIM+k] *= mass_fac;
264 int gmx_nmeig(int argc, char *argv[])
266 const char *desc[] = {
267 "[THISMODULE] calculates the eigenvectors/values of a (Hessian) matrix,",
268 "which can be calculated with [gmx-mdrun].",
269 "The eigenvectors are written to a trajectory file ([TT]-v[tt]).",
270 "The structure is written first with t=0. The eigenvectors",
271 "are written as frames with the eigenvector number as timestamp.",
272 "The eigenvectors can be analyzed with [gmx-anaeig].",
273 "An ensemble of structures can be generated from the eigenvectors with",
274 "[gmx-nmens]. When mass weighting is used, the generated eigenvectors",
275 "will be scaled back to plain Cartesian coordinates before generating the",
276 "output. In this case, they will no longer be exactly orthogonal in the",
277 "standard Cartesian norm, but in the mass-weighted norm they would be.[PAR]",
278 "This program can be optionally used to compute quantum corrections to heat capacity",
279 "and enthalpy by providing an extra file argument [TT]-qcorr[tt]. See the GROMACS",
280 "manual, Chapter 1, for details. The result includes subtracting a harmonic",
281 "degree of freedom at the given temperature.",
282 "The total correction is printed on the terminal screen.",
283 "The recommended way of getting the corrections out is:[PAR]",
284 "[TT]gmx nmeig -s topol.tpr -f nm.mtx -first 7 -last 10000 -T 300 -qc [-constr][tt][PAR]",
285 "The [TT]-constr[tt] option should be used when bond constraints were used during the",
286 "simulation [BB]for all the covalent bonds[bb]. If this is not the case, ",
287 "you need to analyze the [TT]quant_corr.xvg[tt] file yourself.[PAR]",
288 "To make things more flexible, the program can also take virtual sites into account",
289 "when computing quantum corrections. When selecting [TT]-constr[tt] and",
290 "[TT]-qc[tt], the [TT]-begin[tt] and [TT]-end[tt] options will be set automatically as well.",
291 "Again, if you think you know it better, please check the [TT]eigenfreq.xvg[tt]",
295 static gmx_bool bM = TRUE, bCons = FALSE;
296 static int begin = 1, end = 50, maxspec = 4000;
297 static real T = 298.15, width = 1;
300 { "-m", FALSE, etBOOL, {&bM},
301 "Divide elements of Hessian by product of sqrt(mass) of involved "
302 "atoms prior to diagonalization. This should be used for 'Normal Modes' "
304 { "-first", FALSE, etINT, {&begin},
305 "First eigenvector to write away" },
306 { "-last", FALSE, etINT, {&end},
307 "Last eigenvector to write away" },
308 { "-maxspec", FALSE, etINT, {&maxspec},
309 "Highest frequency (1/cm) to consider in the spectrum" },
310 { "-T", FALSE, etREAL, {&T},
311 "Temperature for computing quantum heat capacity and enthalpy when using normal mode calculations to correct classical simulations" },
312 { "-constr", FALSE, etBOOL, {&bCons},
313 "If constraints were used in the simulation but not in the normal mode analysis (this is the recommended way of doing it) you will need to set this for computing the quantum corrections." },
314 { "-width", FALSE, etREAL, {&width},
315 "Width (sigma) of the gaussian peaks (1/cm) when generating a spectrum" }
317 FILE *out, *qc, *spec;
326 real rdum, mass_fac, qcvtot, qutot, qcv, qu;
327 int natoms, ndim, nrow, ncol, count, nharm, nvsite;
329 int i, j, k, l, d, gnx;
333 int version, generation;
334 real value, omega, nu;
335 real factor_gmx_to_omega2;
336 real factor_omega_to_wavenumber;
337 real *spectrum = NULL;
340 const char *qcleg[] = {
341 "Heat Capacity cV (J/mol K)",
342 "Enthalpy H (kJ/mol)"
344 real * full_hessian = NULL;
345 gmx_sparsematrix_t * sparse_hessian = NULL;
348 { efMTX, "-f", "hessian", ffREAD },
349 { efTPX, NULL, NULL, ffREAD },
350 { efXVG, "-of", "eigenfreq", ffWRITE },
351 { efXVG, "-ol", "eigenval", ffWRITE },
352 { efXVG, "-os", "spectrum", ffOPTWR },
353 { efXVG, "-qc", "quant_corr", ffOPTWR },
354 { efTRN, "-v", "eigenvec", ffWRITE }
356 #define NFILE asize(fnm)
358 if (!parse_common_args(&argc, argv, 0,
359 NFILE, fnm, asize(pa), pa, asize(desc), desc, 0, NULL, &oenv))
364 /* Read tpr file for volume and number of harmonic terms */
365 read_tpxheader(ftp2fn(efTPX, NFILE, fnm), &tpx, TRUE, &version, &generation);
366 snew(top_x, tpx.natoms);
368 read_tpx(ftp2fn(efTPX, NFILE, fnm), NULL, box, &natoms,
369 top_x, NULL, NULL, &mtop);
372 nharm = get_nharm(&mtop, &nvsite);
379 top = gmx_mtop_t_to_t_topology(&mtop);
384 if (opt2bSet("-qc", NFILE, fnm))
386 begin = 7+DIM*nvsite;
397 printf("Using begin = %d and end = %d\n", begin, end);
399 /*open Hessian matrix */
400 gmx_mtxio_read(ftp2fn(efMTX, NFILE, fnm), &nrow, &ncol, &full_hessian, &sparse_hessian);
402 /* Memory for eigenvalues and eigenvectors (begin..end) */
403 snew(eigenvalues, nrow);
404 snew(eigenvectors, nrow*(end-begin+1));
406 /* If the Hessian is in sparse format we can calculate max (ndim-1) eigenvectors,
407 * and they must start at the first one. If this is not valid we convert to full matrix
408 * storage, but warn the user that we might run out of memory...
410 if ((sparse_hessian != NULL) && (begin != 1 || end == ndim))
414 fprintf(stderr, "Cannot use sparse Hessian with first eigenvector != 1.\n");
416 else if (end == ndim)
418 fprintf(stderr, "Cannot use sparse Hessian to calculate all eigenvectors.\n");
421 fprintf(stderr, "Will try to allocate memory and convert to full matrix representation...\n");
423 snew(full_hessian, nrow*ncol);
424 for (i = 0; i < nrow*ncol; i++)
429 for (i = 0; i < sparse_hessian->nrow; i++)
431 for (j = 0; j < sparse_hessian->ndata[i]; j++)
433 k = sparse_hessian->data[i][j].col;
434 value = sparse_hessian->data[i][j].value;
435 full_hessian[i*ndim+k] = value;
436 full_hessian[k*ndim+i] = value;
439 gmx_sparsematrix_destroy(sparse_hessian);
440 sparse_hessian = NULL;
441 fprintf(stderr, "Converted sparse to full matrix storage.\n");
444 if (full_hessian != NULL)
446 /* Using full matrix storage */
447 nma_full_hessian(full_hessian, nrow, bM, &top, begin, end,
448 eigenvalues, eigenvectors);
452 /* Sparse memory storage, allocate memory for eigenvectors */
453 snew(eigenvectors, ncol*end);
454 nma_sparse_hessian(sparse_hessian, bM, &top, end, eigenvalues, eigenvectors);
457 /* check the output, first 6 eigenvalues should be reasonably small */
459 for (i = begin-1; (i < 6); i++)
461 if (fabs(eigenvalues[i]) > 1.0e-3)
468 fprintf(stderr, "\nOne of the lowest 6 eigenvalues has a non-zero value.\n");
469 fprintf(stderr, "This could mean that the reference structure was not\n");
470 fprintf(stderr, "properly energy minimized.\n");
473 /* now write the output */
474 fprintf (stderr, "Writing eigenvalues...\n");
475 out = xvgropen(opt2fn("-ol", NFILE, fnm),
476 "Eigenvalues", "Eigenvalue index", "Eigenvalue [Gromacs units]",
478 if (output_env_get_print_xvgr_codes(oenv))
482 fprintf(out, "@ subtitle \"mass weighted\"\n");
486 fprintf(out, "@ subtitle \"not mass weighted\"\n");
490 for (i = 0; i <= (end-begin); i++)
492 fprintf (out, "%6d %15g\n", begin+i, eigenvalues[i]);
497 if (opt2bSet("-qc", NFILE, fnm))
499 qc = xvgropen(opt2fn("-qc", NFILE, fnm), "Quantum Corrections", "Eigenvector index", "", oenv);
500 xvgr_legend(qc, asize(qcleg), qcleg, oenv);
507 printf("Writing eigenfrequencies - negative eigenvalues will be set to zero.\n");
509 out = xvgropen(opt2fn("-of", NFILE, fnm),
510 "Eigenfrequencies", "Eigenvector index", "Wavenumber [cm\\S-1\\N]",
512 if (output_env_get_print_xvgr_codes(oenv))
516 fprintf(out, "@ subtitle \"mass weighted\"\n");
520 fprintf(out, "@ subtitle \"not mass weighted\"\n");
525 if (opt2bSet("-os", NFILE, fnm) && (maxspec > 0))
527 snew(spectrum, maxspec);
528 spec = xvgropen(opt2fn("-os", NFILE, fnm),
529 "Vibrational spectrum based on harmonic approximation",
530 "\\f{12}w\\f{4} (cm\\S-1\\N)",
531 "Intensity [Gromacs units]",
533 for (i = 0; (i < maxspec); i++)
539 /* Gromacs units are kJ/(mol*nm*nm*amu),
540 * where amu is the atomic mass unit.
542 * For the eigenfrequencies we want to convert this to spectroscopic absorption
543 * wavenumbers given in cm^(-1), which is the frequency divided by the speed of
544 * light. Do this by first converting to omega^2 (units 1/s), take the square
545 * root, and finally divide by the speed of light (nm/ps in gromacs).
547 factor_gmx_to_omega2 = 1.0E21/(AVOGADRO*AMU);
548 factor_omega_to_wavenumber = 1.0E-5/(2.0*M_PI*SPEED_OF_LIGHT);
550 for (i = begin; (i <= end); i++)
552 value = eigenvalues[i-begin];
557 omega = sqrt(value*factor_gmx_to_omega2);
558 nu = 1e-12*omega/(2*M_PI);
559 value = omega*factor_omega_to_wavenumber;
560 fprintf (out, "%6d %15g\n", i, value);
563 wfac = eigenvalues[i-begin]/(width*sqrt(2*M_PI));
564 for (j = 0; (j < maxspec); j++)
566 spectrum[j] += wfac*exp(-sqr(j-value)/(2*sqr(width)));
571 qcv = cv_corr(nu, T);
578 fprintf (qc, "%6d %15g %15g\n", i, qcv, qu);
586 for (j = 0; (j < maxspec); j++)
588 fprintf(spec, "%10g %10g\n", 1.0*j, spectrum[j]);
594 printf("Quantum corrections for harmonic degrees of freedom\n");
595 printf("Use appropriate -first and -last options to get reliable results.\n");
596 printf("There were %d constraints and %d vsites in the simulation\n",
598 printf("Total correction to cV = %g J/mol K\n", qcvtot);
599 printf("Total correction to H = %g kJ/mol\n", qutot);
601 please_cite(stdout, "Caleman2011b");
603 /* Writing eigenvectors. Note that if mass scaling was used, the eigenvectors
604 * were scaled back from mass weighted cartesian to plain cartesian in the
605 * nma_full_hessian() or nma_sparse_hessian() routines. Mass scaled vectors
606 * will not be strictly orthogonal in plain cartesian scalar products.
608 write_eigenvectors(opt2fn("-v", NFILE, fnm), natoms, eigenvectors, FALSE, begin, end,
609 eWXR_NO, NULL, FALSE, top_x, bM, eigenvalues);