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The following are not implemented in the current version of PGOPHER, but may be in a future version:

- Spherical Tops
- Nuclear spin effects in symmetric tops are limited to nuclei
on the symmetry axis only.

- Electron spin effects in symmetric tops are partly implemented.
- Magnetic dipole transitions in symmetric tops are partly
implemented

- Internal rotation and other large amplitude motion effects can
only currently be dealt with if the effects are small, and can
be accounted for by adding one or two terms to the Hamiltonian -
see the discussion around the data file nd3x0one.pgo in The pure rotational spectrum of the ground
state of NH
_{3}for an example involving the inversion doubling in ammonia.

- The Mac version is less polished than the windows version. Any problems are, however, likely to affect the user interface only, rather than the calculations. (A comprehensive test suite for the calculations passes on all systems.)

Newer versions of PGOPHER can always read
files from older versions, though design changes may mean some
changes must be made on loading selected files, as noted below.
Older versions can normally read `.pgo `files from newer
versions, though use of new feature can trigger a warning about
unread items. If an error prevents the `.pgo `file from
loading at all in an older version, an ordinary text editor can be
used to remove the problem item if use of an older version is
essential.

- After 8.0.101 calculated angles for an electronic state are shown in degrees, rather than radians.
- After 8.0.186, files with Polarization objects set to something other than the default of 1 will give an error message on loading. This can be ignored, though earlier calculation with such a setting are likely to have been wrong. The rank is now taken from the transition moment.
- To allow all nuclear spin states to be included in calculating
partition functions, the
`SymWt`setting in linear molecules is now (from 8.0.217) included in intensity calculations even for molecules without a centre of symmetry. (This is not normally required, but can be important in, for example, calculations of thermodynamic properties.) To avoid inconsistencies loading data files prepared with older versions of the program will force`SymWt`to 1 for linear molecules without a centre of symmetry. - Versions before 8.0.258 swapped the +
*l*and -*l*labels in symmetric tops for levels of E_{2}and E_{5}vibronic symmetry (not rovibronic symmetry) as compared to the definition given by Hoy and Mills J. Molec Spectrosc. 46, 333 (1973). The calculated energy levels and intensities are not affected, just the labels of the states. Input files for fitting produced by or for older versions may require adjustment for degenerate vibronic states in the affected point groups (D_{4d}and other groups with 5 fold or higher rotation axes). - The
*J*adjusted symmetry handling and associated`JAdjustSym`setting and A+/A- B+/B- symmetry notation was only fully implemented in version 8.0.285. Linelists used for fitting by earlier versions may require adjustment if*J*adjusted symmetry is used in specifying states. (Some of development versions had + and - swapped.) - The method used for determining the assumed origin for
Boltzmann calculations changed in 8.0.333. The
`AssumedOrigin`parameter was introduced allowing this to be explicitly set if required. In addition the logic for linear molecules was slightly adjusted for some cases, which may mean that different results are now obtained if the`IntensityUnits`are set to`Arbitrary`. The difference will only be a constant scale factor (exp(-Δ*E*/*kT*) where Δ*E*is the difference between the old and new origins. - Parameters are scaled by default during fitting in versions
after 8.0.389, as controlled by
`ScaledParameters`.`SVDThresh`, so the default for`SVDThresh`has changed from 10^{-15}to 10^{-6}. The previous behaviour is obtained by setting`ScaledParameters`to false, and this is forced on loading old`.pgo`files if`SVDThresh`is set in the file. - In version 10.0.21 the method of calculation for two photon (and higher rank) transitions in the presence of external fields was changed, and earlier versions will have given wrong results for perpendicular polarization. See Polarization objects for more information.
- In version 10 an adjustment has been made to the phase of some
transition moments; see the discussion at the end of Transition Moments and Line Strengths
for more details. For the most correct calculations
`FixTransitionPhase`should be set to true, and this is likely to become the default. In practice this will not affect most calculations, but may change calculations involving multiple interfering transition moments, particularly if they are of different types. - In version 10.0.502 the default order of
and*J*within a given basis set changed from decreasing to increasing. This can provide better quantum number assignments under some circumstances, though in most cases will have no effect. To force compatibility by reverting to the older order set*F*`OldHyperfineOrder`to`True`.

- New Features in 10.0.505

- Automatic Fitting as
described in "Automatic assignment and fitting of spectra with
`PGOPHER`". There are knock on changes in the Residuals Window, Transitions Window and Line List Window. - Automatic baseline and peak finding; see under Automatic Fitting for worked examples.
- More general lineshape functions - see Lineshape Function and Custom Lineshape Function.
- Forbidden Transition
Moment to allow a wider range of forbidden transitions
to be simulated.

- Bulk Import From Table for
states, transitions and perturbations.

- Import of Excel (.XLS, .XLSX) files and selected other spreadsheet formats, depending on the platform.
- The full set of unicode characters are now handled in many
contexts, though it is recommended that object names are
restricted to the standard ASCII set to avoid problems with
earlier versions of the program.
`PGOPHER`assumes UTF8 encoding in text files in the absence of any other information.

- The default value of MinI
is now 0.01, which typically gives more useful Fortrat plots
as many weak transitions are excluded.

- Initial implementation of import of Bruker Opus files
(typically *.0).

- Initial implementation of handling of spectra in FITS format, common
for astronomical data.

- Text file overlay import faster and more robust, and will
also import comment lines from the start of the file.

- In the overlay menu, "
`Deglitch`" is now "`Delete point`", and "`Delete Points`" command has been added. - On-line help is now connected on Linux and Mac.

- Enhancements to SPFIT/SPCAT file handling - see the qfmt and
MapState directives.

- Significant speed-ups for selected operations, particularly handling large line lists and experimental data files.
- LAPACK upgraded to 3.6.1
- "
`Offset By...`" menu item on manifolds to shift all state origins by a constant amount. - Stack traces on non-windows systems now show in the log window, rather than the console.
- More consistent keyboard shortcuts in Mac version.
- Overlay linelists can include estimated error values; these
are not plotted, but if the peak finder finds a single peak
the value will be copied to the "
`Std Dev`" column in the linelist window.

- Fixed Problems in 10.0.505

- An adjustment has been made to the phase of some transition
moments; see the discussion at the end of Transition Moments and Line
Strengths for more details. For the most correct
calculations
`FixTransitionPhase`should be set to true *M*dependent line strengths for perpendicular multiphoton transitions. See Polarization objects for more information.- Change in definition of spin forbidden gS; now discards quantum number dependence
- Changing units changes increment as well as value and standard deviation
- On non-windows machines, save and restore of a setup with multiple plot windows open gave a (harmless) error message.
- Colours lost in line list window.

- New Features in 9.1.100

- Comprehensive tutorial Walkthrough of
Simulating and Fitting a Simple Spectrum added to the
documentation, including an N
_{2}O sample spectrum to work with.

- Custom Width Functions provide an alternative simple empirical way of specifying quantum number dependent line widths and intensities.
- Significant rework of the Transitions Window to allow selection by more quantum numbers and other options.
- BranchExpr format added as an option to the linelist window.
- Remove forced sorting of transition moments by rank.

- Settings set to
`Auto`have the actual value displayed in the hint in the constants window and in detailed line listings. - Rename parameter command added to the Variables object, and others to which parameters can be added.
`makesvn`script to give a starting point for compiling`PGOPHER`if the available binaries are not suitable.- Updated fundamental constants to the CODATA 2014 set from http://physics.nist.gov.
The largest effect of this is a to scale effective absolute
temperatures by 1.000000274, the amount by which
*k*/*h*has changed. - Atomic masses taken from v4.1 of the NIST "Atomic Weights and Isotopic Compositions" at http://physics.nist.gov/PhysRefData/Compositions
- LAPACK upgraded to 3.6.0
`MaxDJ`setting for Linear, Symmetric, Asymmetric Top nuclei to limit the maximum Δ*J*to consider in evaluating hyperfine matrix elements.- Fixed Problems in 9.1.100
- Disable global menu on Ubuntu Unity for
`PGOPHER`, as it interacts badly with the multiple windows used.

- Speed up rejection of vibrational states above
`Emax`.

- All Button on plot now resets vertical scale as well as the
horizontal scale.

- If
`Signed`of a Custom Transition Function was`True`the function was called twice, both with and without the signed quantum numbers. The is only an issue if the`Value`variable was used.

`Copy Branch Table`/`Copy Simple Format`and corresponding fits in the linelist window fixed for linear case for several combinations of`ShowOmega`,`ShowFNumber`and`Showef`.- Transitions window would show 4th power of transformed transition matrix elements if transition moments with multiple ranks contributed to it, rather than the square as labelled.
- In Transitions window
update symmetry names if molecule
`JAdjustSym`setting is changed.

- Fixed Problems in 9.0.101

- Better handling of multiple spin 0 nuclei on
`.par`/`.var`import. - Some error messages in Mac version resulted in crash.

- New Features in 9.0.100

- Vibrational
Partition Function for calculating complete partition
functions.

- Command line export of Hamiltonian and
transition matrices.

- Scale relative magnitudes of parameters when fitting, based
on the derivatives. This is controlled by the
`ScaledParameters`setting.

- Switch memory manager to FastMM,
which is significantly faster on some workloads. In addition
changes have been made to the code that gives significant
speed-ups for large problems on multi-core machines.

- Export to CSV
file added as option in right clicking an object in the constants window.

`AssumedOrigin`parameter to override automatic estimate of this.

`OmegaOrder`setting to override automatic mechanism for assigning Ω,*N*and F number in linear molecules.

*l*-matrix and other vibrational calculation windows have an option to rotate the plot plane about the axis plotted horizontally. (A full 3D plot option is planned for the next version.)

- More plot options in the Residuals
window, including ratios and logarithmic scales most useful
when fitting intensities, and the population option now works.

- zMatrix has a show calculated
parameters menu command.

- A+ and A- (and B+/B-) notation for symmetry alternating with
*J*in Symmetric Tops.

- IntensityUnits
directive in observation files to specify the units of
intensity observations.

- Default Symmetry in
observations files can be specified as either
*J*adjusted or non*J*adjusted.

- Branches in linelists for fitting can be expressed in a more
general way using the BranchExpr
directive, to allow easy adjustment to assignments.

- Custom Population
functions now have
`EB`and`Origin`variables, to allow a closer match to the`PGOPHER`calculation.

- Simple calculator for testing expressions.

- Table object for use with
expressions.

- Objects having an expression, such as Custom Population
Functions or Custom
Transition Functions now display with an enlarged (and
correctly labelled) window in the Constants
Window.

- OscillatorStrength
is now an intensity option.

- Sub-basis numbers can be included in the quantum number
display.

- The
`SymWt`setting in linear molecules is now included in intensity calculations even for molecules without a centre of symmetry to allow all nuclear spins to be included in partition function calculations.

- The size of matrix that the 64 bit version can handle is now limited by available memory, rather than 16384×16384.
- Check Derivatives
option to fitting to assess the accuracy of numerical
derivatives, and other tools to assist in fitting.

- Branch format
allows specification of symmetry for symmetric tops.

- Setting SVDThresh
negative switches the least squares process to a QR
factorisation method.

- Simple line list format extended for symmetric tops, and
other fixes to
*K*quantum number handling, including branch format input. See the`SymmetryLabels`and`CompactKLabels`flags. As part of this fix Copy simple format from the linelist window now works for symmetric tops.

- Detailed output now includes simulation parameters, and
fundamental constants used.

- Custom populations can now specify an M dependence in the
presence of external field, either in a custom population
function, or as numerical populations specfied in a manifold.

- Force constants in internal coordinates can now specify the
electronic states they operate on, allowing for Jahn-Teller or
similar terms that act between electronic states to be
handled.

- Added zero point rotational constants Bx0, By0 and Bz0 to
calculated parameters for an electronic state. These and the
inertial defect are calculated to avoid problems with
resonances for zero point level, as in A. L. L. East, C. S.
Johnson and W. D. Allen, J. Chem. Phys.
**98**, 1299 (1993).

- Switched fundamental constants to CODATA 2010 set (was 2006
set). This has a small effect, most significantly on
intensities. (A temperature of 300.000375 K is required to
reproduce earlier spectra at 300 K).

- Threshold for zero frequency vibrational modes and other
small values now adjustable via
`SmallCoefficient`. - Loomis-Wood plots.

- Debug setting added to Custom Population functions and Custom Transition Moment functions.
- Angstroms (or Å) now a valid unit.

- LAPACK upgraded to 3.5.0
- Correlations object now
always written to .pgo file if present. (It was not in version
8 to avoid compatibility problems with earlier versions.)

- Fixed Problems in 9.0.100

- Adjusted treatment of exclude perturbations flag when plotting observed energy levels.
- Negative Error
Multiplier in energy level plots scales errors by the
estimated error of the observation.

- Inconsistent observation colours in level
and residual plots.

- Improve F1/F2/F3 numbering and
*N*assignment if`OmegaSelect`is used for linear molecules. Note that unexpected results are still possible - see the documentation for`OmegaSelect`. - If Symmetry
Coordinates are used the largest coefficient in the
**L**matrix for a given mode is forced positive by multiplying the mode by -1. This helps to give consistent signs for Coriolis coupling constants and some other values.

- Equivalent nuclei with spin 0 that have been explicitly
included in the calculation now have the correct statistical
weight applied. As part of this fix, the irrelevant Spin and
AsNext settings were removed from nuclei for vibrational
calculations.

- The I
_{2}built in calibration overlay was broken.

- Hönl-London checkbox disabled in Transitions Window if external fields present, as it does not do a relevant calculation.
- Documentation for
`Scomp`values for linear perturbations was wrong - values in text were doubled.

- Width setting in
vibrational simulations was treated incorrectly.

- +
*l*and -*l*labels were swapped in symmetric tops for levels of E_{2}and E_{5}vibronic symmetry (not rovibronic symmetry) as compared to the definition given by Hoy and Mills J. Molec Spectrosc. 46, 333 (1973). - Specifying individual level
populations failed when overall
*J*was half integral.

*l*matrix import from molpro was not handling dummy atoms.

- Complex transition moment matrices were not displayed
correctly in the transition moments window.

- The RemoveSpins
directive was not correctly removing all terms involving
electron spin.

- Display of symmetric
top perturbations in constants tree inverted if
`lChange`not zero.

- Convert to Perturbations for symmetric tops corrupted zeta.

- Branch format linelists failed for linear molecules with
hyperfine structure.

- HITRAN files for O
_{2}, NO and OH would not import; ignore lines not beginning with a number.

- Spectra in the presence of external fields involving
symmetric tops with degenerate vibronic states included
spurious extra transitions.

*M*dependence of multiphoton transitions always used 1 as the transition rank, giving incorrect intensities in the presence of an external field. As part of the fix for this Rank has been removed as a setting in Polarization objects; the rank is now taken from the transition moment. In addition spectra with random polarisation in the presence of an external field had the wrong relative intensity between Δ*M*= 0 and Δ*M*≠ 0 for all ranks.

- Energy level lists of a single state in a manifold only show
levels assigned to that state.

- Display of vibrations fails in the presence of dummy atoms.

- Force failure when redundant coordinates used and
**UU**^{T}=**1**test fails.

- Do not decompose Dushinsky
Matrix into equivalent rotations if determinant
negative.

**G**^{-1}matrix printed out incorrectly

- Force field analysis printout used two different meanings
for the
**A**matrix.

- Documentation wrong for
`FixCentre`.

- Allow
`FrequencyOffset`and`FrequencyScale`to be set in a .ovr file at the same time as a calibration function.

- Remove order dependence of node fixup.

- Fixed crash on level printout if widths present.

- Peak finding reported positions to insufficient precision
for spectra with a very non-uniform frequency scale, such as
spectra arising from combining non-adjacent individual
spectra.

- Custom Population
functions and Custom
Transition Moment functions used ½ the required
values for the Fn variable.

- Precision lost in Voigt profile on some platforms

- Units directive more
flexible: accepts
`cm1`, nmVac, nmAir, angVac, angAir, Angstroms. (Previous versions had no way of specifying air wavelengths.) - Fixes for compilation using the free Pascal compiler under
windows.

- Fixed Problems in 8.0.102

- Calculated angles for a state more than 138.5 degrees shown as 180-angle. In fixing this, the angle display has been changed to degrees, rather than radians.
- Level and states window crash on Mac (only), and fixed some layout issues.
- Inconsistent results depending on whether the Internal Coordinates and related windows displayed or not.
- Fixed inconsistent use of Principal axis system in selected vibrational calculations.
- Molden import of
*l*matrix files now normalizes all the normal co-ordinates.

- New Features in 8.0.100

- Tweaks for Mac usage, including more (Mac) standard shortcut
keys and dropping of files onto main window.

- Much increased flexibility in the use of HITRAN files.
- ExoMol files can be used
in a variety of ways by
`PGOPHER`.

- Added η and γ
_{S}terms to the linear molecule Hamiltonian. These are required for some states with*S*> 1.

- Custom Transition
Moment Function provides a more general way of modeling
any
*J*dependence of the transition moment, replacing the`C`and`D`parameters of Transition Moment objects. Data files containing non-zero`C`or`D`values are converted to use this automatically on loading.

- Axis Switching effects can now
be simulated.

- More symbolic matrix elements - selected transition moments,
...

- half spin Vibrational calculation.

- Open shell symmetric tops.
- Documented lambda doubling for delta and higher states.

`scalestddev`directive in fit files to allow relative standard deviations to be set as a fraction of the observed value - mainly intended for fitting intensities.

`removespins`directive in fit files now works for intensity fits, as well as line position fits.

- Linelist window has many more options - fit as branch format, save as branch format.
- A Variables object can be used
to add dummy parameters for constrained fits.

- Constrained parameters are forced to be not floated as part
of the fit setup process.

- Level Window now has option to
use
*J*(*J*+1) for the*x*axis, rather than just*J*.

- Rename of Molecule or Manifold will offer the option of
making the required name change in the linelist window.

- Simplified line list format extended to be more flexible for
linear molecules, and to allow fitting to levels as well as
transitions.

- Right click on Molecule or Manifold now offers "Energy Level List" option, sorted by symmetry or energy, and "Partition Function Table" which prints out a table of partition functions for the selected node as a function of temperature. It will also display the fraction of partition function due to levels up to the level set in "Level List by energy".
- The numerical data from many files produced by Origin (.OPJ
files) can now be read.

- Print out of Stark or Zeeman shifts now estimates linear, quadratic field shifts and fits to an intermediate two level model.
- When plotting parts of an overall spectrum, the different
coloured spectra are always plotted in a consistent order.

- Images from many PDF files can now be read as a bitmap overlay.

- UsePopParams as an
alternative, per manifold, way of setting the use of numerical
populations.

- The vertical range of both overlays and simulations can now
optionally be set, rather than always auto scaling. This is
controlled by the AutoMin and AutoMax settings in overlays and
simulations. The toolbar on the main window has been updated
to provide some control over these.

- Consistent handling of imaginary operators for asymmetric
tops.

- LAPACK upgraded to 3.4.2

- Symbolic matrix elements and convert to perturbation now
implemented for symmetric tops.

- Initial implementation of custom population
functions.

- Initial implementation of D
_{3}, D_{4}... D_{8}point groups for symmetric tops.

- Compact of a bitmap now prompts for a threshold.
- When simulating spectra in the presence of a static electric or magnetic field, the partition function is now calculated with static fields on, rather than at zero field.
- 64 bit version (using unicode internally) now part of the
standard release.

- Fixed Problems in in 8.0.100
- When importing
*l*matrices from Gaussian output, read both the "Input orientation" and "Standard orientation" atomic co-ordinates and use the most recent set when reading vibrations to allow files produced with the "nosymm" flag to be read.

- Very low temperatures (~0.01 K or less) could cause some
transitions to be missed if
`Tspin`is not the default. An error message is now printed in these circumstances.

- Spin forbidden transition moments in linear molecules were
incorrectly giving zero intensity for
*q*= 0 components in certain circumstances. The definition of the`Strength`parameter has been adjusted to fix this.

- Added progress indicator to constructing large vibrational
bases to allow abort on large problems.

- The import of the
*l*matrix from Molden or Molpro files now assumes average mass for nuclei, rather than the exact mass for the most abundant isotope. In addition a different set of atomic co-ordinates is taken from Molpro xml files, as the one originally chosen did not use a consistent axis system. For all*l*matrix imports an orthogonality check is done and a message displayed if the result is too large.

- Default
`vMax`for a Vibrational Mode is now zero, unless there are 3 or less modes, in which case it is 3. This prevents triggering a very large calculation by accident; the default was 5 for all modes.

- Line list output - column headed S is actually
*S*_{pol}- change header appropriately.

- Linear Perturbations with
`Scomp`<> 0 were not displayed correctly in the object treeview.

- Contour fits now permit undefined values for the observed
intensity.

- Fix crash of following use of recently opened files on Mac
by replacing TdfsMRUFileList component with simplified
equivalent.

- Switching units scales
`Displacement`in VibrationModeChange does not change spectrum. (Effective units are 1/Sqrt(Energy)).

- Move Up/Move Down of plots in overlays window was ignored
until overlay file saved and reloaded.

- Level Window gave corrupt plots
if a very small vertical range was selected.

- Transitions Window was not
showing matrices for selected transitions in the vibration
only mode.

- Selected transitions omitted for the unusual point groups C
_{3h}...C_{6h}(involving states with E symmetry) and S_{4}...S_{12}(for non totally symmetric states) point groups.

- Force use of "." for decimal point, even if changed for
system while program running. (This is required so that data
files are not language dependent.)

- Fix blank edit boxes on main window toolbar if system font
set to large on Windows.

- Matrix printout in log window for high print levels could
crash.

- Equivalent nuclei case handled incorrectly in presence of
static field.

- Degeneracies printed incorrectly in level lists in presence of static electric or magnetic field.
- Einstein A
coefficient printed incorrectly in line lists if the plot
units were different to the calculation units.

- Covert units button on constants form failed when AsNext set for equivalent nuclei.
- Statistical weights calculated incorrectly for the case of
more than one pair of equivalent nuclei when hyperfine
structure was included.

- Hyperfine structure with more than one set of equivalent
nuclei, or different nuclei using an equivalent coupling
scheme like I
_{12}= I_{1}+ I_{2}; F_{2}= J + I_{12}; I_{34}= I_{3}+ I_{4}; F = F_{2}+ I_{34}was not calculated correctly.

- Potentially complex fine and hyperfine terms in asymmetric tops were not necessarily handled correctly. This affects "off-diagonal" terms such as eabbar, Tab and CHIab. This is fixed by the introduction of consistent handling of imaginary operators for asymmetric tops.
- Fixes for symbolic matrix elements for asymmetric tops
(Origin and BBar).

- State dependent widths (wK, wJ) for symmetric tops were ignored.

- "Another" button on level plot was broken.

- Energy level fit to lower level failed if no default
manifold.