PCM (pulse-code modulation) is the simplest way to store sound digitally. A microphone signal is measured thousands of times per second, and each measurement — a sample — is written down as a number. Play those numbers back at the same rate through a speaker and you get the original sound. Every WAV file, every CD and nearly every audio interface works with PCM internally; MP3, AAC and Opus are compressed formats that are decoded back to PCM before you hear them.
A raw .pcm file is just those numbers, one after another, with nothing else in the file. There is no header saying how many samples per second there are, how many bytes each sample occupies, or whether left and right channels are interleaved. Three facts fully describe the data — sample rate, bit depth (with its encoding and byte order), and channel count — and all three have to come from somewhere other than the file itself: the device documentation, the API that produced it, or trial and error.
PCM vs WAV: the 44-byte difference
A WAV file is PCM with a small RIFF header in front, usually 44 bytes long. That header stores exactly the three facts a raw file is missing, which is why any media player can open a WAV but almost none can open a .pcm. If you strip the header from a 16-bit WAV, what remains is a valid raw PCM file. If you are unsure what you have, open the file in a hex editor: a WAV starts with the ASCII characters RIFF and contains WAVE at byte 8. If you see those, rename the file to .wav and open it normally.
Why VLC and Windows Media Player refuse to play it
Media players identify files by looking for a known header or container signature. A headerless file has none, so the player either reports an unsupported format or guesses and plays noise. Some desktop tools can decode raw PCM if you supply the parameters by hand, which is useful once you have found the right settings here:
# VLC
vlc --demux=rawaud --rawaud-channels=1 --rawaud-samplerate=16000 --rawaud-fourcc=s16l file.pcm
# FFmpeg's player (mono, 16-bit signed little-endian, 16 kHz)
ffplay -f s16le -ar 16000 file.pcm
# Audacity: File → Import → Raw Data…, then pick encoding, byte order, channels and rate