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OCR Text

DEC - 12-1.^5 AJune, 1970

The material in this handbook, including but not
limited to instruction times and operating speeds,
is for information purposes and is subject to change
i t h o u t notice.

v-7

The following are trademarks of Digital Equipment
Corporation, Maynard, Massachusetts:

DEC
FLIP CHIP
DIGITAL

PDP
FOCAL
COMPUTER LAB

The equipment described herein is covered by patents
and patents pending.

Eor additional copies order DEC-12~UW5A--D from Program
Library, Digital Equipment Corporation, 146 Main Street,
Maynard, Mass.
01754
Price $a..00

TABLE OF CONTENTS

1 . 0

ABSTlViCT

2. 0

EQUIPMENT

3.0

OPERATING PROCEDURES

4.0

SPECTRUM GENERATION
Comments
Paper Tape I/O

4 ^ 1
4

4. 4
4. 5

4.6
4. 7

2
2
2

Spins
Offset & Width
Chemical Shift
Coupling Constants
Block and Unit

2
2
3
o

5.4
5»5
5.6

COMMANDS
Restart
Coupling Constants
Offset & Width
DIAL
List
Punch

6.0

OPERATING SUGGESTIONS

5 . 0
5 . 1

5.2
5

7.0

8.0

3
4
4
4
4

NMR B7^CKGR0UND

EXAMPLE
6

9.0

10.0

ASSEMBLING NMRSIM

INTERNAL DESCRIPTION

1. 0

ABSTRACT

nMRSIM(E)

is designed to calculate theoretical spectra of compounds containing nuclei of spin one-half including hydrogen, fluorine, and carb6n-13.
Chemical shifts for each nucleus and coupling constants between nuclei are
'

input from the Teletype*

Calculated line spectra are displayed on the VR12
calibration points are displayed across the X axis. Output is to LINCtape and high- or lovz-speed paper tape punch, as well as to
the TelotypG.
NMRSIM has options that allow varying all the parameters as
well as offsets for enhancement of resolution.
Chemical shifts and coupling
constants may be adjusted continuously until the displayed theoretical spectrum is acceptable.
Spectra may be read back and displayed from LINCtape or
scope.

T^/zenty-f ive

paper tape; several psectra may be meryed in this mode of operation, thereby
allowing the simulation of large spin systems or mixtures of compounds.
2.0

EQUIPMENT

A PDP-12A equipped with KW12A real time clock and MC12 4K Memory Extension is required.
3.0

OPERATING PROCEDURES

NMRSIM (E)

loaded from

LAP6-DIAL^ tape containing the program by the command

LO NMRSIM (E) ,0

)

Refer to the LAP6-DIAL Programmer's Manual, DEC-12-SE2B-D for further details.
The restarting procedure is as follows:

Press the STOP key on the PDP-12A.
Press I/O PRESET.

Press START.

NMRSIM then returns to the display mode.
1

NMRSIME utilizes the EAE option for the PDP-12.
2

LAP6-DIAL is hereafter referred to as DIAL.

4.0

SPECTRUM GENERATION

After the program is loaded, it prints a series of messages on the Teletype
to specialize the parameters for the experiment.
The user types a .reply to

each message and terminates the response by pressing the RETURN ke^-.
If an
illegal response is typed, a ? is printed on the Teletype and the rr.essage'is
repeated.
The RUBOUT key can be used to erase incorrectly typed characters
before a terminator is typed.
The messages are listed below with their ac-

ceptable responses.
4 . 1

Refer to section 8.0 for a sample dialogue.

COMMENTS

Any amount of commentary can be typed at this time using any of the Teletype
keys.
After entering appropriate titles, type CTRL/A to advance to the next
message.

4 . 2

WANT PAPER TAPE I/O?

Only a response of Y or N is acceptable.
A reply of N stores the position
and intensity of all calculated transitions on LINCtape only.
A reply of
Y outputs the position and intensity of all calculated transitions
on paper
tape in addition to LINCtape.
After a reply of Y, a second question is

printed

WANT HIGH SPEED READER-PUNCH?
Type Y to use the high-speed punch, type N to output to the Teletype punch.
4.3

NO. OF SPINS =

Enter the nximber of spins; values from
4.4

OFFSET

through

are acceptable.

WIDTH

These two parameters define the range of the X axis on the scope.
OFFSET
is the value in Hz of the first point rinplayed along the horizontal axis.
WIDTH is thr, total range in llz of t.ho horizontal axis.
It is important

mind that the axis will bod splayed from right to leFt corresponding to th(.t standard display mocJo for NMR dai.ci.
to

kr;cr^

4 . 5

CHEMICAL SHIFTS

Enter the value

m Hz of the CHEMICAL SHIFTS in order.

Type a comma to

separate values:
1,
4. 6

COUPLING CONSTANTS

Enter the value in Hz of the coupling constants in order:
2,

^1 3,

^^1

^In,

^2 4,

Sjjecify every coupling constant required,

Type

4 . 7

BLOCK, U:

^2n,

^Cn-l)n

even if the value is zero.

comma after each value.

Type the starting block in octal notation, a comma, and the number of
the LINCtape transport unit to be used to store the peak parameters of
the calculated transitions.
The number of blocks required is dependent
upon the size of the spin system desired.
The computer now calculates the theoretical spectra and automatically
stores the data on the LINCtape.
5 . 0

COMMANDS

When dis[. laying a line spectrum the Teletype is active and can be used
to issue comrnrinds defining the next task for the computer.
Six options
are available to the user at this time.
Each of these commands is issued
by typing the appropriate letter follov/ed by a colon.
The command may be
changed by using the RUBOUT key before the colon has been typed. The displ
can be scaled v/ith Right Switches 9, 10 and 11.
3. 1

(RESTART)

Restart prints the message COMMENTS (section 4.1) and restarts the program.
It is used to calculate a complete set of new data.
Note that
paper tape status can not be changed after the initial responses to the

messages

5.2

(COUPLING CO'I^STAMTS

Returns to section 4,6 and requests

nev/

Used for open loop

parameters.

iteration to find the best coupling constants.
5.3

O (OFFSET

WIDTH)

This command allows a new section of the X axis to be displayed on the

scope so that any section of the calculated spectrum can be displayed
on the scope.

The OFFSET option is useful for resolution enhancement.

To exercise this. option, there must be NMR data on LINCtape or paper
tape (prepared by the P: command).
If paper tape was requested during
initialization (section 4.2), the question

TAPE INPUT?
is

Type Y to road data from the high speed or Teletype reader and

asked.

v/rite it on LlllCtapc before display.

^ , 4

Type N to read data from LINCtape.

(DIAL;

Program returns control to the DIAL Operating System.
5 . 5

(LIST

The L command lists intensity and energy data on the Teletype in tabular
format.

After typing

MIN.
is printed.

the message

INTENSITY:

Type an integer number betv^een 0 and 1000.

of the transition is greater than the entered value

intensities that are listed,

the scope.

'fype

A second question

DISPLAY LIST

Typo

is thr;n priritrjr].

If the intensity

the transition will

This question thus serves as a threshold on the

be in the output list.

output

(.)ri

output all linos

the lines

the

wh. ich

tta}^le»

di.s[)layed on

fire

There are usually

many more lines than are displayed on the scope because the scope cannot

resolve closely adjacent lines.

If the Teletype punch is turned on during a List operation
a binary
coded decimal paper tape is produced v;hich may be used as inpu.t to CATACAL
(DEC~12--UW1A-D) to produce a spectrum consisting of peaks instead of lines.
^

5.6

(PUNCH)

The accumulated spectrum can be punched on the high-speed reader/punch
by issuing the punch conimand.

OPEIWriMG SUGGESTIONS

6. 0

A useful starting point for many 60 MHz NMR (hydrogen)

spectra of organic
molecules is a sweep offset of 0 Hz and a sweep width of 500 Hz,
For best
results, however, all peaks should eventually be examined at a considerably
smaller sv/eep width, since rounding errors may give misleading scope displays with large sweep widths*
It should be noted that increasing the sweep

offset moves peaks to the right, and decreasing the sweep offset moves peaks
to the left.
Once the peaks are observed, the proper sweep offset and width
can be determined from the 25 calibration marks placed across the X axis.
For purposes of estimating a logical minimum intensity, remember that the
calibration on the scope on the Y axis is always 0 to 1000.
1

NMR BACKGROUND

The discussion below assumes that the nuclei being studied are hydrogen,
fluorine, carbon- 13 or other nuclei of: spin 1/2.

Each nucleus in a rriolocule can be assigned a spin of ei.ther a or 3
For
a syHt^:m containiny n nuclcj
there are
spin states |)Ossible.
Each of
these states is called a basic product function.
The energy of a basic
product function can be calculated from equation 1 belov/ where s^ = -1/2
.

for

spin and + 1/2 for

Hz, Tj^j-

1/4 if

posite spin, and

spin,

is the frequency of absorption in

and j have the same spin and

i
J\.

1/4 if

the coupling constant between

and

have op-

in cps.

n
1

3>i

)

The energy of interaction between two basic product functions is 0 unless
both have the same number of
a and B
spins
V^hen this condition is fulfilled, the interaction energy i.s calculated from equation 2 where U=l if
the basic product functions differ only in the interchange of spins i and
«

(J.j

as de-fined above).

1/2U]

Otherwise.!,

\y-^0.

Thus,

to calculate an NMR spectrum,

constructs all of the possible

one^

basic product functions and sorts them into groups, each member of
group containing the same number of a and

spins.

The energy of .sach

of them is determined and used as the diagnonal element in a square matrix.
The of f "diagonal elements of this matrix

matrix)

action botv/een the members of the group.

are energies of inter-

This matrix is diagonalized and

these elements then contain the energies of the final spin functions.

These final spin eigenf unctions are the columns of the matrix (U matrix)

required to diagonalize the H matrix.

Each element in a spin function

represents the contribution of a basic product function to that spin
function
Before continuing, it is necessary to define the

value of a spin func-

tion, as shown in equation 3, where s^ is as previously defined.
= P

Nov/

i=l

the peaks observed in NMR spectra are transitions from one spin func-

tion to anothor.

Those transition Gnorgies and their intensities can be

oalculrjted as outlined bolov;.

tions v/hose

F^^

Transitions are allowed between spin func-

values differ only by

If this holds,

the energy of the

transition is the difference in energy of the final spin eigenf unctions
and the intensity of the transition is given by equation
uth element in one spin function,

where

8.0

Otherwise,
(Z

is the

is the vth element in the other spin

function, and A-1 if the basic product functions represented by

differ by one spin.

C^^

and

A==j3.

c C*A)^

U V

EXAMPLE

The following pages represent an actual printout.

sentations of those displayed on the scope.
typed by the usr^r.

The spectra are repre-

The underlined data is that

LO NMRSIME,2

NMRSIM
COMMENTS
WAIIT

DJ-MO

PAPER TAPE I/0?Y

WANT HIGH SPEED READER-PUNCH?y
NO, OF SPINS=

OFFSET

WIDTH

CHEMICAL SHIFTS:

50^

9j2f ,

COUPLING CONSTANTS:
BLOCK, U:

9j0 , 9j0 , 26^ , 260

^ / Jg

3 . 8 , 0 , 8 , 8 , 8 , 8 , JZI

4 00,

J
L:

MIN.

INTENSITY :0

DISPLAY LIST?Y
INTENSITY
27.00
90.00
9 9.00
36.00
104.00
189.00
86.00

ENERGY
272.0.0

264.00
256.00
248.00
97.00
90.00
81.00

Pj
0:"

OFFSET

WIDTH J2f,

3jglj2f

TAPE INPUT?Y_
BLOCK,

42jg,3,

M0RE7N^
P:

NMRSIM
COMMENTS:

DEMO

NO. OF SPINS=

OFFSET

CONT

WIDTH ;^j_5g£

CHEMICAL SHIFTS:

265,280

coupling; COiJSTAriTS:

J:iLOCK.,

f~r-T-T

4 40,3

r "T

-T

—

i--r -r- t"T"i

-y-r-r-

—

C^
COUPLING CONSTANTS:
LLOCK,

(J:

440_,3_

TAPE ir]PUT?N
BLOCK, U:

440,3

KORE?N

T-T

r-T

9.0

ASSEMBLING NMRSIM

The NMRSIM program is supplied to the user in both source and binary on
the tape.
To generate a new binary file if the source program is modified,
use the following procedure.

Load a DIAL-MS tape on unit 0,
Load unit 1 with either
a DIAL*-V2 or DIAL-MS system tape.
If another tape unit
is aval Labia, mount the tape containing the CLEARSYM and

MMRSTM source programs there.
IP only' two tape units
are a va l.able^ p ace the sourer; programs on unit 0 (with
PIP if riocossary), in order to reduce the assembly time.
i.

Type ^ZK ^

Type ->AS CLLARSYM ^
CLEARSYM is a two word program
which produces a clean symbol table.

to clear the binary V?orking Area of unit

^000
SAVSYM
4.

Type
>AS NMR2,0^
Krror messages generated at this
time should be ignored.
Press the RETURN key to terminate the assembly after the errors have all been printed to suppress printing of the symbol table.
,

Typo

>-7>eJ ,

This clears the binary Working AmsL on unit

Typo
.LI IJMR3,0j.
If no listing is desired, use the AS
command.
Any errors generated now are real and must be
corrected

Type
->-LI
NMR2,0^
Because the symbol table produced is
the same as the one generated in step 6, printing may be
suppressed with the RETURN key after it has started to be
printed.

Type -SB NMR23,0}
This saves the binary output from the
two previous assemblies

Type

10.

-^ZeJ

Two versions of the Floating Point Packacjo are aipplied
If the raachine has the KAE option, NMRIL should bo used
in the following steps and NMI^STMK v/ill bo generated.
If the machine does nothave this option, NMRl should be
used to generate NMRSIM.

11.

Type -AB NMRl

12,

Type -AB NMR2 3,jef J

13.

Type -^B NMRSIM.^PJ
A binary file of NMRSIM(E) has now
been gencreitecl and tiB command ->L0 NMRSIM,0 ^. will cause
load and. execute.

INTERNAL DESCRIPTION

10.0

The complete program listings are contained at the back of
the manual.
The
following is a brief outline of the program; capital letters below
refer to

variables

Begins with text mode for input of commentary.

Enter the number of spins and store in N.

Set "switch" for punched output.

Set up basic produce functions

(BPFs).

Calculate HARRY array v;hich contains relative addresses
of the BPFs of different F value.

Calculate NUSE array.
This array actually contains the
BPFs.
They are stored in groups, each group having an
value one greater than the preceding group.

Get sweep offset and sweep width.

Get chemical shifts.

Get coupling constants.

Initialize SPEC array.
A.

This array eventually contains the displayed spectrum.

It is initialized to jd except for calibration points
where it is set to 4000^.
o

Calculate first H and U matrices.
A.

First H matrix is always

10.

First U matrix is always
equal to 1.

which does not require

X 1 with its only element

di agona 1 i z a tion

Set FLAG which is the negatlvo of the number of times the
loop from 11 to 17 must be executed.

11.

Set N2, calculate EN and UOLD arrays.
A.

Copy the trace of the H matrix into the EN array,

Copy the U matrix into the UOLD array.

Set N2 equal to the size of the H matrix just copied.

12.

Calculate the size of the next H matrix and put in into Nl.

13.

Determine which transitions will be allowed between the
EPFs represented by UOLD and those that will be represented
by U.
This is stored in the array called TABLE.

14.

Initial izo

and U matrixes.

Diagonal H elements are calculated by equation

Off-diagonal

The U a-nahrlx is initialized to all zeros except for
ones on the diagonal.

elements are calculated by equation

15.

Diagonalize the 11 matrix and calculate the U matrix by
the Jacobi method.

16.

Calculate transitions,

17.

18.

Calculate transition energies by forming the differences between the elements of the trace of the H matrix and the elements in the EN array.

Calculate transition intensities from equation

Store appropriate values in SPEC array.

Test FLAG to see if the loop is done.
loop is not done, go to 11,

If loop is done, display spectrum,

If ALT MODE is typed, interpret mnemonic and execute
option.

Assembling NMRSIM., 10
Block Number,

Chemical Shifts,
Conimands

Coupling Constants,
DIAL,

Equipment,
Example, 6

Intensi ty 4
Internal Description,
,

List,

I'lessages

Offset, 2, 4
Operating Procedure,

Paper Tape 1/0,
Punch, 5

Restart Procedure,
RUBOUT, 2

Spectrum Generation,
Spins,

Width,

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